Polarizing, photochromic devices and methods of making the same

ABSTRACT

Provided is a composite optical element including:
         a substrate;   an at least partially ordered polymeric sheet connected to at least a portion of the substrate; and   at least one thermally reversible photochromic-dichroic compound that is at least partially aligned with at least a portion of the at least partially ordered polymeric sheet and has an average absorption ratio greater than 2.3 in the activated state.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a division of U.S. patent application Ser. No.10/846,650, filed May 17, 2004 now U.S. Pat. No. 7,256,921.

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT

Not applicable.

REFERENCE TO A SEQUENCE LISTING

Not applicable.

BACKGROUND

Various embodiments disclosed herein relate generally to opticalelements, security liquid crystal cells and methods of making the same.

Conventional, linearly polarizing elements, such as linearly polarizinglenses for sunglasses and linearly polarizing filters, are typicallyformed from stretched polymer sheets containing a dichroic material,such as a dichroic dye. Consequently, conventional linearly polarizingelements are static elements having a single, linearly polarizing state.Accordingly, when a conventional linearly polarizing element is exposedto either randomly polarized radiation or reflected radiation of theappropriate wavelength, some percentage of the radiation transmittedthrough the element will be linearly polarized. As used herein the term“linearly polarize” means to confine the vibrations of the electricvector of light waves to one direction or plane.

Further, conventional linearly polarizing elements are typically tinted.That is, conventional linearly polarizing elements contain a coloringagent (i.e., the dichroic material) and have an absorption spectrum thatdoes not vary in response to actinic radiation. As used herein “actinicradiation” means electromagnetic radiation, such as but not limited toultraviolet and visible radiation that is capable of causing a response.The color of the conventional linearly polarizing element will dependupon the coloring agent used to form the element, and most commonly, isa neutral color (for example, brown or gray). Thus, while conventionallinearly polarizing elements are useful in reducing reflected lightglare, because of their tint, they are not well suited for use undercertain low-light conditions. Further, because conventional linearlypolarizing elements have only a single, tinted linearly polarizingstate, they are limited in their ability to store or displayinformation.

As discussed above, conventional linearly polarizing elements aretypically formed using sheets of stretched polymer films containing adichroic material. As used herein the term “dichroic” means capable ofabsorbing one of two orthogonal plane polarized components of at leasttransmitted radiation more strongly than the other. Thus, while dichroicmaterials are capable of preferentially absorbing one of two orthogonalplane polarized components of transmitted radiation, if the molecules ofthe dichroic material are not suitably positioned or arranged, no netlinear polarization of transmitted radiation will be achieved. That is,due to the random positioning of the molecules of the dichroic material,selective absorption by the individual molecules will cancel each othersuch that no net or overall linear polarizing effect is achieved. Thus,it is generally necessary to suitably position or arrange the moleculesof the dichroic material by alignment with another material in order toachieve a net linear polarization.

One common method of aligning the molecules of a dichroic dye involvesheating a sheet or layer of polyvinyl alcohol (“PVA”) to soften the PVAand then stretching the sheet to orient the PVA polymer chains.Thereafter, the dichroic dye is impregnated into the stretched sheet anddye molecules take on the orientation of the polymer chains. That is,the dye molecules become aligned such that the long axis of the dyemolecule are generally parallel to the oriented polymer chains.Alternatively, the dichroic dye can be first impregnated into the PVAsheet, and thereafter the sheet can be heated and stretched as describedabove to orient the PVA polymer chains and associated dye. In thismanner, the molecules of the dichroic dye can be suitably positioned orarranged within the oriented polymer chains of the PVA sheet and a netlinear polarization can be achieved. That is, the PVA sheet can be madeto linearly polarize transmitted radiation, or in other words, alinearly polarizing filter can be formed.

In contrast to the dichroic elements discussed above, conventionalphotochromic elements, such as photochromic lenses that are formed usingconventional thermally reversible photochromic materials are generallycapable of converting from a first state, for example a “clear state,”to a second state, for example a “colored state,” in response to actinicradiation, and reverting back to the first state in response to thermalenergy. As used herein the term “photochromic” means having anabsorption spectrum for at least visible radiation that varies inresponse to at least actinic radiation. Thus, conventional photochromicelements are generally well suited for use in both low-light and brightconditions. However, conventional photochromic elements that do notinclude linearly polarizing filters are generally not adapted tolinearly polarize radiation. That is, the absorption ratio ofconventional photochromic elements, in either state, is generally lessthan two. As used herein the term “absorption ratio” refers to the ratioof the absorbance of radiation linearly polarized in a first plane tothe absorbance of the same wavelength radiation linearly polarized in aplane orthogonal to the first plane, wherein the first plane is taken asthe plane with the highest absorbance. Therefore, conventionalphotochromic elements cannot reduce reflected light glare to the sameextent as conventional linearly polarizing elements. Further,conventional photochromic elements have a limited ability to store ordisplay information.

Accordingly, it would be advantageous to provide elements and devicesthat are adapted to display both linearly polarizing and photochromicproperties. Further, it would be advantageous to provide elements anddevices that are adapted to display circular or elliptical polarizationand photochromic properties.

BRIEF SUMMARY OF THE DISCLOSURE

Various non-limiting embodiments disclosed herein relate to opticalelements. For example, one non-limiting embodiment provides an opticalelement comprising an at least partial coating having a first state anda second state connected to at least a portion of a substrate, the atleast partial coating being adapted to switch from the first state tothe second state in response to at least actinic radiation, to revertback to the first state in response to thermal energy, and to linearlypolarize at least transmitted radiation in at least one of the firststate and the second state.

Another non-limiting embodiment provides an optical element comprising asubstrate, and at least one at least partially aligned thermallyreversible photochromic-dichroic compound connected to at least aportion of the substrate and having an average absorption ratio greaterthan 2.3 in an activated state as determined according to CELL METHOD.

Still another non-limiting embodiment provides an optical elementcomprising a substrate, at least one at least partially orderedorientation facility connected to at least a portion of the substrate,and an at least partial coating connected to at least a portion of theat least partially ordered orientation facility, the at least partialcoating comprising at least one at least partially ordered anisotropicmaterial and at least one photochromic-dichroic compound that is atleast partially aligned with at least a portion of the at leastpartially ordered anisotropic material.

Yet another non-limiting embodiment provides an optical elementcomprising a substrate, a first at least partial coating comprising anat least partially ordered alignment medium connected to at least aportion of at least one surface of the substrate, a second at leastpartial coating comprising an alignment transfer material that isconnected to and at least partially aligned with at least a portion ofthe at least partially ordered alignment medium, and a third at leastpartial coating connected to at least a portion of the alignmenttransfer material, the third at least partial coating comprising atleast one anisotropic material that is at least partially aligned withat least a portion of the at least partially aligned alignment transfermaterial and at least one photochromic-dichroic compound that is atleast partially aligned with at least a portion of the at leastpartially aligned anisotropic material.

Other non-limiting embodiments relate to composite optical elements. Forexample, one non-limiting embodiment provides a composite opticalelement comprising a substrate, an at least partially ordered polymericsheet connected to at least a portion of the substrate, and at least onethermally reversible photochromic-dichroic compound that is at leastpartially aligned with at least a portion of the at least partiallyordered polymeric sheet and has an average absorption ratio greater than2.3 in the activated state as determined according to CELL METHOD.

Another non-limiting embodiment provides a composite optical elementcomprising a substrate, and at least one sheet connected to at least aportion of the substrate, the at least one sheet comprising an at leastpartially ordered liquid crystal polymer having at least a first generaldirection, at least one at least partially ordered liquid crystalmaterial having at least a second general direction that is generallyparallel to at least the first general direction distributed within atleast a portion of the liquid crystal polymer, and at least onephotochromic-dichroic compound that is at least partially aligned withat least a portion of the at least one at least partially ordered liquidcrystal material.

Still other non-limiting embodiments relate to methods of making opticalelements. For example, one non-limiting embodiment provides a method ofmaking an optical element comprising forming an at least partial coatingcomprising at least one at least partially aligned thermally reversiblephotochromic-dichroic compound on at least a portion of a substrate.

Another non-limiting embodiment provides a method of making an opticalelement comprising: (a) forming an at least partial coating on at leasta portion of a substrate, and (b) adapting at least a portion of the atleast partial coating to switch from a first state to a second linearlypolarizing state in response to actinic radiation and to revert back tothe first sate in response to thermal energy.

Still another non-limiting embodiment provides a method of making anoptical element comprising: forming an at least partial coatingcomprising an alignment medium to at least a portion of at least onesurface of a substrate and at least partially ordering at least aportion of the alignment medium, forming at least one at least partialcoating comprising an alignment transfer material on at least a portionof the at least partial coating comprising the alignment medium and atleast partially aligning at least a portion of the alignment transfermaterial with at least a portion of the at least partially orderedalignment medium, and forming an at least partial coating comprising ananisotropic material and at least one photochromic-dichroic compound onat least a portion of the alignment transfer material, at leastpartially aligning at least a portion of the anisotropic material withat least a portion of the at least partially aligned alignment transfermaterial, and at least partially aligning at least a portion of the atleast one photochromic-dichroic compound with at least a portion of theat least partially aligned anisotropic material.

Still another non-limiting embodiment provides a method of making acomposite element comprising connecting an at least partially orderedpolymeric sheet to at least a portion of a substrate, the at leastpartially ordered polymeric sheet comprising at least one at leastpartially aligned thermally reversible photochromic-dichroic compoundconnected to at least a portion thereof and having an average absorptionratio greater than 2.3 in an activated state as determined according toCELL METHOD.

Yet another non-limiting embodiment provides a method of making acomposite element comprising: forming a sheet comprising an at leastpartially ordered liquid crystal polymer having at least a first generaldirection, a liquid crystal material having at least a second generaldirection distributed within at least a portion of the liquid crystalpolymer; and at least one photochromic-dichroic compound that is atleast partially aligned with at least portion of the liquid crystalmaterial; and connecting at least a portion of the sheet to at least aportion of an optical substrate to form the composite element.

Still another non-limiting embodiment provides a method of making acomposite element comprising forming a sheet comprising an at leastpartially ordered liquid crystal polymer having at least a first generaldirection and a liquid crystal material having at least a second generaldirection distributed within at least a portion of the liquid crystalpolymer, connecting at least a portion of the sheet to at least aportion of an optical substrate, and imbibing at least onephotochromic-dichroic compound into at least a portion of the sheet.

Another non-limiting embodiment provides a method of making an opticalelement comprising overmolding an at least partial coating comprising anat least partially ordered liquid crystal material and at least one atleast partially aligned photochromic-dichroic compound on at least aportion of an optical substrate.

Still another non-limiting embodiment provides a method of making anoptical element comprising overmolding an at least partial coatingcomprising an at least partially ordered liquid crystal material on atleast a portion of an optical substrate; and imbibing at least onephotochromic-dichroic compound into at least a portion of the at leastpartially ordered liquid crystal material.

Other non-limiting embodiments relate to security elements. For example,one non-limiting embodiment provides a security element connected to atleast a portion of a substrate, the security element comprising an atleast partial coating having a first state and a second state connectedto at least a portion of the substrate, the at least partial coatingbeing adapted to switch from a first state to a second state in responseto at least actinic radiation, to revert back to the first state inresponse to thermal energy, and to linearly polarize at leasttransmitted radiation in at least one of the first state and the secondstate.

Another non-limiting embodiment provides a method of making a securityelement comprising forming an at least partial coating on at least aportion of the substrate, the at least partial coating comprising atleast one at least partially aligned, thermally reversiblephotochromic-dichroic compound.

Other non-limiting embodiments relate to liquid crystal cells. Forexample, one non-limiting embodiment provides a liquid crystal cellcomprising a first substrate having a first surface, a second substratehaving a second surface, wherein the second surface of the secondsubstrate is opposite and spaced apart from the first surface of thefirst substrate so as to define an region, and a liquid crystal materialadapted to be at least partially ordered and at least one thermallyreversible photochromic-dichroic compound adapted to be at leastpartially aligned and having an average absorption ratio greater than2.3 in an activated state as determined according to CELL METHODpositioned within the region defined by the first surface and the secondsurface.

Another non-limiting embodiment provides an optical element comprising asubstrate; and an at least partial coating having a first state and asecond state on at least a portion of the substrate, the at leastpartial coating being adapted to be circularly polarizing orelliptically polarizing in at least one state and comprising a chiralnematic or cholesteric liquid crystal material having molecules that arehelically arranged through a thickness of the at least partial coating,and at least one photochromic-dichroic compound that is at leastpartially aligned with the liquid crystal material such that a long axisof a molecule of the at least one photochromic-dichroic compound isgenerally parallel to the molecules of the liquid crystal material.

Another non-limiting embodiment provides an optical element a substrate;and an at least partial coating connected to at least a portion of thesubstrate, the at least partial coating comprising an at least partiallyordered anisotropic material and at least one photochromic-dichroiccompound that is at least partially aligned with the at least partiallyordered anisotropic material, said photochromic-dichroic compoundcomprising: (a) at least one photochromic group chosen from a pyran, anoxazine, and a fulgide; and (b) at least one lengthening agent Lattached to the at least one photochromic group and represented by:—[S₁]_(c)-[Q₁-[S₂]d]d′-[Q₂-[S₃]_(e)]_(e′)-[Q₃-[S₄]_(f)]_(f′)—S₅—Pwhich is set forth herein below in detail.

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING(S)

Various non-limiting embodiments of the present invention will be betterunderstood when read in conjunction with the drawings, in which:

FIG. 1 shows two average difference absorption spectra obtained for acoating according to various non-limiting embodiment disclosed herein;and

FIG. 2 is a schematic, cross-sectional view of an overmolding assemblyaccording to one non-limiting embodiment disclosed herein.

DETAILED DESCRIPTION OF EMBODIMENTS

As used in this specification and the appended claims, the articles “a,”“an,” and “the” include plural referents unless expressly andunequivocally limited to one referent.

Additionally, for the purposes of this specification, unless otherwiseindicated, all numbers expressing quantities of ingredients, reactionconditions, and other properties or parameters used in the specificationare to be understood as being modified in all instances by the term“about.” Accordingly, unless otherwise indicated, it should beunderstood that the numerical parameters set forth in the followingspecification and attached claims are approximations. At the very least,and not as an attempt to limit the application of the doctrine ofequivalents to the scope of the claims, numerical parameters should beread in light of the number of reported significant digits and theapplication of ordinary rounding techniques.

Further, while the numerical ranges and parameters setting forth thebroad scope of the invention are approximations as discussed above, thenumerical values set forth in the Examples section are reported asprecisely as possible. It should be understood, however, that suchnumerical values inherently contain certain errors resulting from themeasurement equipment and/or measurement technique.

Optical elements and devices according to various non-limitingembodiments of the present invention will now be described. Variousnon-limiting embodiments disclosed herein provide an optical elementcomprising an at least partial coating having a first state and a secondstate connected to at least a portion of at least one surface of asubstrate, the at least partial coating being adapted to switch from thefirst state to the second state in response to at least actinicradiation, to revert back to the first state in response to thermalenergy, and to linearly polarize at least transmitted radiation in atleast one of the first state and the second state. As used herein, theterm “thermal energy” means any form of heat.

As used herein to modify the term “state,” the terms “first” and“second” are not intended to refer to any particular order orchronology, but instead refer to two different conditions or properties.For example, although not limiting herein, the first state and thesecond state of the coating may differ with respect to at least oneoptical property, such as but not limited to the absorption or linearlypolarization of visible and/or UV radiation. Thus, according to variousnon-limiting embodiments disclosed herein, the at least partial coatingcan be adapted to have a different absorption spectrum in each of thefirst and second state. For example, while not limiting herein, the atleast partial coating can be clear in the first state and colored in thesecond state. Alternatively, the at least partial coating can be adaptedto have a first color in the first state and a second color in thesecond state. Further, as discussed below in more detail, the at leastpartial coating can be adapted to not be linearly polarizing (or“non-polarizing”) in the first state and linearly polarizing in thesecond state.

As used herein the term “optical” means pertaining to or associated withlight and/or vision. For example, according to various non-limitingembodiments disclosed herein, the optical element or device can bechosen from ophthalmic elements and devices, display elements anddevices, windows, mirrors, and active and passive liquid crystal cellelements and devices. As used herein the term “ophthalmic” meanspertaining to or associated with the eye and vision. Non-limitingexamples of ophthalmic elements include corrective and non-correctivelenses, including single vision or multi-vision lenses, which may beeither segmented or non-segmented multi-vision lenses (such as, but notlimited to, bifocal lenses, trifocal lenses and progressive lenses), aswell as other elements used to correct, protect, or enhance(cosmetically or otherwise) vision, including without limitation,contact lenses, intra-ocular lenses, magnifying lenses, and protectivelenses or visors. As used herein the term “display” means the visible ormachine-readable representation of information in words, numbers,symbols, designs or drawings. Non-limiting examples of display elementsand devices include screens, monitors, and security elements, such assecurity marks. As used herein the term “window” means an apertureadapted to permit the transmission of radiation therethrough.Non-limiting examples of windows include automotive and aircrafttransparencies, filters, shutters, and optical switches. As used hereinthe term “mirror” means a surface that specularly reflects a largefraction of incident light.

As used herein the term “liquid crystal cell” refers to a structurecontaining a liquid crystal material that is capable of being ordered.Active liquid crystal cells are cells wherein the liquid crystalmaterial is capable of being switched between ordered and disorderedstates or between two ordered states by the application of an externalforce, such as electric or magnetic fields. Passive liquid crystal cellsare cells wherein the liquid crystal material maintains an orderedstate. One non-limiting example of an active liquid crystal cell elementor device is a liquid crystal display.

As discussed above, one non-limiting embodiment provides, in part, anoptical element comprising an at least partial coating having a firststate and a second state connected to at least a portion of at least onesurface of a substrate. As used herein the term “coating” means asupported film derived from a flowable composition, which may or may nothave a uniform thickness, and specifically excludes polymeric sheets. Asused herein the term “sheet” means a pre-formed film having a generallyuniform thickness and capable of self-support. Further, as used hereinthe term “connected to” means in direct contact with an object orindirect contact with an object through one or more other structures ormaterials, at least one of which is in direct contact with the object.Thus, according to various non-limiting embodiments disclosed herein,the at least partial coating having the first state and the second statecan be in direct contact with at least a portion of the substrate or itcan be in indirect contact with at least a portion of the substratethrough one or more other structures or materials. For example, althoughnot limiting herein, the at least partial coating can be in contact withone or more other at least partial coatings, polymer sheets orcombinations thereof, at least one of which is in direct contact with atleast a portion of the substrate.

Generally speaking, substrates that are suitable for use in conjunctionwith various non-limiting embodiments disclosed herein include, but arenot limited to, substrates formed from organic materials, inorganicmaterials, or combinations thereof (for example, composite materials).Non-limiting examples of substrates that can be used in accordance withvarious non-limiting embodiments disclosed herein are described in moredetail below.

Specific, non-limiting examples of organic materials that may be used toform the substrates disclosed herein include polymeric materials, forexamples, homopolymers and copolymers, prepared from the monomers andmixtures of monomers disclosed in U.S. Pat. No. 5,962,617 and in U.S.Pat. No. 5,658,501 from column 15, line 28 to column 16, line 17, thedisclosures of which U.S. patents are specifically incorporated hereinby reference. For example, such polymeric materials can be thermoplasticor thermoset polymeric materials, can be transparent or optically clear,and can have any refractive index required. Non-limiting examples ofsuch disclosed monomers and polymers include: polyol(allyl carbonate)monomers, e.g., allyl diglycol carbonates such as diethylene glycolbis(allyl carbonate), which monomer is sold under the trademark CR-39 byPPG Industries, Inc.; polyurea-polyurethane (polyurea-urethane)polymers, which are prepared, for example, by the reaction of apolyurethane prepolymer and a diamine curing agent, a composition forone such polymer being sold under the trademark TRIVEX by PPGIndustries, Inc.; polyol(meth)acryloyl terminated carbonate monomer;diethylene glycol dimethacrylate monomers; ethoxylated phenolmethacrylate monomers; diisopropenyl benzene monomers; ethoxylatedtrimethylol propane triacrylate monomers; ethylene glycolbismethacrylate monomers; poly(ethylene glycol)bismethacrylate monomers;urethane acrylate monomers; poly(ethoxylated bisphenol Adimethacrylate); poly(vinyl acetate); poly(vinyl alcohol); poly(vinylchloride); poly(vinylidene chloride); polyethylene; polypropylene;polyurethanes; polythiourethanes; thermoplastic polycarbonates, such asthe carbonate-linked resin derived from bisphenol A and phosgene, onesuch material being sold under the trademark LEXAN; polyesters, such asthe material sold under the trademark MYLAR; poly(ethyleneterephthalate); polyvinyl butyral; poly(methyl methacrylate), such asthe material sold under the trademark PLEXIGLAS, and polymers preparedby reacting polyfunctional isocyanates with polythiols or polyepisulfidemonomers, either homopolymerized or co- and/or terpolymerized withpolythiols, polyisocyanates, polyisothiocyanates and optionallyethylenically unsaturated monomers or halogenated aromatic-containingvinyl monomers. Also contemplated are copolymers of such monomers andblends of the described polymers and copolymers with other polymers, forexample, to form block copolymers or interpenetrating network products.

While not limiting herein, according to various non-limiting embodimentsdisclosed herein, the substrate can be an ophthalmic substrate. As usedherein the term “ophthalmic substrate” means lenses, partially formedlenses, and lens blanks. Non-limiting examples of organic materialssuitable for use in forming ophthalmic substrates according to variousnon-limiting embodiments disclosed herein include, but are not limitedto, the art-recognized polymers that are useful as ophthalmicsubstrates, e.g., organic optical resins that are used to prepareoptically clear castings for optical applications, such as ophthalmiclenses.

Other non-limiting examples of organic materials suitable for use informing the substrates according to various non-limiting embodimentsdisclosed herein include both synthetic and natural organic materials,including without limitation: opaque or transluscent polymericmaterials, natural and synthetic textiles, and cellulosic materials suchas, paper and wood.

Non-limiting examples of inorganic materials suitable for use in formingthe substrates according to various non-limiting embodiments disclosedherein include glasses, minerals, ceramics, and metals. For example, inone non-limiting embodiment the substrate can comprise glass. In othernon-limiting embodiments, the substrate can have a reflective surface,for example, a polished ceramic substrate, metal substrate, or mineralsubstrate. In other non-limiting embodiments, a reflective coating orlayer can be deposited or otherwise applied to a surface of an inorganicor an organic substrate to make it reflective or to enhance itsreflectivity.

Further, according to certain non-limiting embodiments disclosed herein,the substrates may have a protective coating, such as, but not limitedto, an abrasion-resistant coating, such as a “hard coat,” on theirexterior surfaces. For example, commercially available thermoplasticpolycarbonate ophthalmic lens substrates are often sold with anabrasion-resistant coating already applied to its exterior surfacesbecause these surfaces tend to be readily scratched, abraded or scuffed.An example of such a lens substrate is the GENTEX™ polycarbonate lens(available from Gentex Optics). Therefore, as used herein the term“substrate” includes a substrate having a protective coating, such asbut not limited to an abrasion-resistant coating, on its surface(s).

Still further, the substrates according to various non-limitingembodiments disclosed herein can be untinted, tinted, linearlypolarizing, circularly polarizing, elliptically polarizing,photochromic, or tinted-photochromic substrates. As used herein withreference to substrates the term “untinted” means substrates that areessentially free of coloring agent additions (such as, but not limitedto, conventional dyes) and have an absorption spectrum for visibleradiation that does not vary significantly in response to actinicradiation. Further, with reference to substrates the term “tinted” meanssubstrates that have a coloring agent addition (such as, but not limitedto, conventional dyes) and an absorption spectrum for visible radiationthat does not vary significantly in response to actinic radiation.

As used herein the term “linearly polarizing” with reference tosubstrates refers to substrates that are adapted to linearly polarizeradiation. As used herein the term “circularly polarizing” withreference to substrates refers to substrates that are adapted tocircularly polarize radiation. As used herein the term “ellipticallypolarizing” with reference to substrates refers to substrates that areadapted to elliptically polarize radiation. As used herein with the term“photochromic” with reference to substrates refers to substrates havingan absorption spectrum for visible radiation that varies in response toat least actinic radiation. Further, as used herein with reference tosubstrates, the term “tinted-photochromic” means substrates containing acoloring agent addition as well as a photochromic material, and havingan absorption spectrum for visible radiation that varies in response toat least actinic radiation. Thus, for example and without limitation,the tinted-photochromic substrate can have a first color characteristicof the coloring agent and a second color characteristic of thecombination of the coloring agent the photochromic material when exposedto actinic radiation.

As previously discussed, conventional linearly polarizing elements aretypically formed using stretched polymer sheets and a dichroic dye.However, these conventional linearly polarizing elements generally havea single tinted, linearly polarizing state. As previously discussed, theterm “linearly polarize” means to confine the vibrations of the electricvector of light waves to one direction. Further, as previouslydiscussed, conventional photochromic elements are formed fromconventional photochromic compounds and have at least two states, forexample a clear state and a colored state. As previously discussed, theterm “photochromic” means having an absorption spectrum for at leastvisible radiation that varies in response to at least actinic radiation.However, conventional photochromic elements are generally not adapted tolinearly polarize radiation.

As discussed above, the optical elements according to variousnon-limiting embodiments disclosed herein comprise an at least partialcoating having a first state and a second state that is adapted toswitch from the first state to the second state in response to actinicradiation, to revert back to the first state in response to thermalenergy, and to be linearly polarizing in at least one of the first stateand the second state. That is, the optical elements according to variousnon-limiting embodiments disclosed herein can be photochromic-dichroicelements. As used herein the term “photochromic-dichroic” meansdisplaying both photochromic and dichroic (i.e., linearly polarizing)properties under certain conditions, which properties are at leastdetectible by instrumentation. Further, as discussed below in moredetail, the optical elements according to various non-limitingembodiments disclosed herein can be formed using at least onephotochromic-dichroic compound that is at least partially aligned.

As previously mentioned, according to various non-limiting embodimentsdisclosed herein, the at least partial coating can be adapted to benon-polarizing in the first state (that is, the coating will not confinethe vibrations of the electric vector of light waves to one direction)and to linearly polarize at least transmitted radiation in the secondstate. As used herein the term “transmitted radiation” refers toradiation that is passed through at least a portion of an object.Although not limiting herein, the transmitted radiation can beultraviolet radiation, visible radiation, or a combination thereof.Thus, according to various non-limiting embodiments disclosed herein,the at least partial coating can be adapted to be non-polarizing in thefirst state and to linearly polarize transmitted ultraviolet radiation,transmitted visible radiation, or a combination thereof in the secondstate.

According to still other non-limiting embodiments, the at least partialcoating having a first state and a second state can be adapted to have afirst absorption spectrum in the first state, a second absorptionspectrum in the second state, and to be linearly polarizing in both thefirst and second states.

According to one non-limiting embodiment, the at least partial coatinghaving the first state and the second state can have an averageabsorption ratio of at least 1.5 in at least one state. According toanother non-limiting embodiment, the at least partial coating can havean average absorption ratio ranging from at least 1.5 to 50 (or greater)in at least one state. As previously discussed, the term “absorptionratio” refers to the ratio of the absorbance of radiation linearlypolarized in a first plane to the absorbance of radiation linearlypolarized in a plane orthogonal to the first plane, wherein the firstplane is taken as the plane with the highest absorbance. Thus, theabsorption ratio (and the average absorption ratio which is describedbelow) is an indication of how strongly one of two orthogonal planepolarized components of radiation is absorbed by an object or material.

The average absorption ratio of a coating or element comprising aphotochromic-dichroic compound can be determined as set forth below. Forexample, to determine the average absorption ratio of a coatingcomprising a photochromic-dichroic compound, a substrate having acoating is positioned on an optical bench and the coating is placed in alinearly polarizing state by activation of the photochromic-dichroiccompound. Activation is achieved by exposing the coating to UV radiationfor a time sufficient to reach a saturated or near saturated state (thatis, a state wherein the absorption properties of the coating do notsubstantially change over the interval of time during which themeasurements are made). Absorption measurements are taken over a periodof time (typically 10 to 300 seconds) at 3 second intervals for lightthat is linearly polarized in a plane perpendicular to the optical bench(referred to as the 0° polarization plane or direction) and light thatis linearly polarized in a plane that is parallel to the optical bench(referred to as the 90° polarization plane or direction) in thefollowing sequence: 0°, 90°, 90°, 0° etc. The absorbance of the linearlypolarized light by the coating is measured at each time interval for allof the wavelengths tested and the unactivated absorbance (i.e., theabsorbance of the coating in an unactivated state) over the same rangeof wavelengths is subtracted to obtain absorption spectra for thecoating in an activated state in each of the 0° and 90° polarizationplanes to obtain an average difference absorption spectrum in eachpolarization plane for the coating in the saturated or near-saturatedstate.

For example, with reference to FIG. 1, there is shown the averagedifference absorption spectrum (generally indicated 10) in onepolarization plane that was obtained for a coating according to onenon-limiting embodiment disclosed herein. The average absorptionspectrum (generally indicated 11) is the average difference absorptionspectrum obtained for the same coating in the orthogonal polarizationplane.

Based on the average difference absorption spectra obtained for thecoating, the average absorption ratio for the coating is obtained asfollows. The absorption ratio of the coating at each wavelength in apredetermined range of wavelengths corresponding to λ_(max-vis)±5nanometers (generally indicated as 14 in FIG. 1), wherein λ_(max-vis) isthe wavelength at which the coating had the highest average absorbancein any plane, is calculated according to the following equation:AR_(λi)=Ab¹ _(λi)/Ab² _(λi)  Eq. 1wherein, AR_(λi) is the absorption ratio at wavelength λ_(i), Ab¹ _(λi)is the average absorption at wavelength λ_(i) in the polarizationdirection (i.e., 0° or 90°) having the higher absorbance, and Ab² _(λi)is the average absorption at wavelength λ_(i) in the remainingpolarization direction. As previously discussed, the “absorption ratio”refers to the ratio of the absorbance of radiation linearly polarized ina first plane to the absorbance of the same wavelength radiationlinearly polarized in a plane orthogonal to the first plane, wherein thefirst plane is taken as the plane with the highest absorbance.

The average absorption ratio (“AR”) for the coating is then calculatedby averaging the individual absorption ratios over the predeterminedrange of wavelengths (i.e., λ_(max-vis)±5 nanometers) according to thefollowing equation:AR=(ΣAR _(λi))/n _(i)  Eq. 2wherein, AR is average absorption ratio for the coating, AR_(λi) are theindividual absorption ratios (as determined above in Eq. 1) for eachwavelength within the predetermined range of wavelengths, and n_(i) isthe number of individual absorption ratios averaged. A more detaileddescription of this method of determining the average absorption ratiois provided in the Examples.

As previously mentioned, according to various non-limiting embodimentsdisclosed herein, the at least partial coating having the first stateand the second state can comprise at least one photochromic-dichroiccompound that is at least partially aligned. As previously discussed,the term “photochromic-dichroic” means displaying both photochromic anddichroic (i.e., linearly polarizing) properties under certainconditions, which properties are at least detectible by instrumentation.Accordingly, “photochromic-dichroic compounds” are compounds displayingboth photochromic and dichroic (i.e., linearly polarizing) propertiesunder certain conditions, which properties are at least detectible byinstrumentation. Thus, photochromic-dichroic compounds have anabsorption spectrum for at least visible radiation that varies inresponse to at least actinic radiation and are capable of absorbing oneof two orthogonal plane polarized components of at least transmittedradiation more strongly than the other. Additionally, as withconventional photochromic compounds discussed above, thephotochromic-dichroic compounds disclosed herein can be thermallyreversible. That is, the photochromic-dichroic compounds can switch froma first state to a second state in response to actinic radiation andrevert back to the first state in response to thermal energy. As usedherein the term “compound” means a substance formed by the union of twoor more elements, components, ingredients, or parts and includes,without limitation, molecules and macromolecules (for example polymersand oligomers) formed by the union of two or more elements, components,ingredients, or parts.

For example, according to various non-limiting embodiments disclosedherein, the at least one photochromic-dichroic compound can have a firststate having a first absorption spectrum, a second state having a secondabsorption spectrum that is different from the first absorptionspectrum, and can be adapted to switch from the first state to thesecond state in response to at least actinic radiation and to revertback to the first state in response to thermal energy. Further, thephotochromic-dichroic compound can be dichroic (i.e., linearlypolarizing) in one or both of the first state and the second state. Forexample, although not required, the photochromic-dichroic compound canbe linearly polarizing in an activated state and non-polarizing in thebleached or faded (i.e., not activated) state. As used herein, the term“activated state” refers to the photochromic-dichroic compound whenexposed to sufficient actinic radiation to cause the at least a portionof the photochromic-dichroic compound to switch from a first state to asecond state. Further, although not required, the photochromic-dichroiccompound can be dichroic in both the first and second states. While notlimiting herein, for example, the photochromic-dichroic compound canlinearly polarize visible radiation in both the activated state and thebleached state. Further, the photochromic-dichroic compound can linearlypolarize visible radiation in an activated state, and can linearlypolarize UV radiation in the bleached state.

Although not required, according to various non-limiting embodimentsdisclosed herein, the at least one photochromic-dichroic compound canhave an average absorption ratio of at least 1.5 in an activated stateas determined according to the CELL METHOD. According to othernon-limiting embodiments disclosed herein, the at least onephotochromic-dichroic compound can have an average absorption ratiogreater than 2.3 in an activated state as determined according to theCELL METHOD. According to still other non-limiting embodiments, the atleast one at least partially aligned photochromic-dichroic compound canhave an average absorption ratio ranging from 1.5 to 50 in an activatedstate as determined according to the CELL METHOD. According to othernon-limiting embodiments, the at least one at least partially alignedphotochromic-dichroic compound can have an average absorption ratioranging from 4 to 20, can further having an average absorption ratioranging from 3 to 30, and can still further having an average absorptionratio ranging from 2.5 to 50 in an activated state as determinedaccording to the CELL METHOD. However, generally speaking, the averageabsorption ratio of the at least one at least partially alignedphotochromic-dichroic compound can be any average absorption ratio thatis sufficient to impart the desired properties to the device or element.Non-limiting examples of suitable photochromic-dichroic compounds aredescribed in detail herein below.

The CELL METHOD for determining the average absorption ratio of thephotochromic-dichroic compound is essentially the same as the methodused to determine the average absorption ratio of the at least partialcoating (described above and in the Examples), except that, instead ofmeasuring the absorbance of a coated substrate, a cell assemblycontaining an aligned liquid crystal material and thephotochromic-dichroic compound is tested. More specifically, the cellassembly comprises two opposing glass substrates that are spaced apartby 20 microns±1 micron. The substrates are sealed along two oppositeedges to form a cell. The inner surface of each of the glass substratesis coated with a polyimide coating, the surface of which has been atleast partially ordered by rubbing. Alignment of thephotochromic-dichroic compound is achieved by introducing thephotochromic-dichroic compound and the liquid crystal medium into thecell assembly, and allowing the liquid crystal medium to align with therubbed polyimide surface. Once the liquid crystal medium and thephotochromic-dichroic compound are aligned, the cell assembly is placedon an optical bench (which is described in detail in the Examples) andthe average absorption ratio is determined in the manner previouslydescribed for the coated substrates, except that the unactivatedabsorbance of the cell assembly is subtracted from the activatedabsorbance to obtain the average difference absorption spectra.

As previously discussed, while dichroic compounds are capable ofpreferentially absorbing one of two orthogonal components of planepolarized light, it is generally necessary to suitably position orarrange the molecules of a dichroic compound in order to achieve a netlinear polarization effect. Similarly, it is generally necessary tosuitably position or arrange the molecules of a photochromic-dichroiccompound to achieve a net linear polarization effect. That is, it isgenerally necessary to align the molecules of the photochromic-dichroiccompound such that the long axis of the molecules of thephotochromic-dichroic compound in an activated state are generallyparallel to each other. Therefore, as discussed above, according tovarious non-limiting embodiments disclosed herein, the at least onephotochromic-dichroic compound is at least partially aligned. Further,if the activated state of the photochromic-dichroic compound correspondsto a dichroic state of the material, the at least onephotochromic-dichroic compound can be at least partially aligned suchthat the long axis of the molecules of the photochromic-dichroiccompound in the activated state are aligned. As used herein the term“align” means to bring into suitable arrangement or position byinteraction with another material, compound or structure.

Further, although not limiting herein, the at least partial coating cancomprise a plurality of photochromic-dichroic compounds. Although notlimiting herein, when two or more photochromic-dichroic compounds areused in combination, the photochromic-dichroic compounds can be chosento complement one another to produce a desired color or hue. Forexample, mixtures photochromic-dichroic compounds can be used accordingto certain non-limiting embodiments disclosed herein to attain certainactivated colors, such as a near neutral gray or near neutral brown.See, for example, U.S. Pat. No. 5,645,767, column 12, line 66 to column13, line 19, the disclosure of which is specifically incorporated byreference herein, which describes the parameters that define neutralgray and brown colors. Additionally or alternatively, the at leastpartial coating can comprise mixtures of photochromic-dichroic compoundshaving complementary linear polarization states. For example, thephotochromic-dichroic compounds can be chosen to have complementarylinear polarization states over a desired range of wavelengths toproduce an optical element that is capable of polarizing light over thedesired range of wavelengths. Still further, mixtures of complementaryphotochromic-dichroic compounds having essentially the same polarizationstates at the same wavelengths can be chosen to reinforce or enhance theoverall linear polarization achieved. For example, according to onenon-limiting embodiment, the at least partial coating having the firststate and the second state can comprise at least two at least partiallyaligned photochromic-dichroic compounds, wherein the at least two atleast partially aligned photochromic-dichroic compounds have at leastone of: complementary colors and complementary linear polarizationstates.

As previously discussed, various non-limiting embodiments disclosedherein provide an optical element comprising an at least partial coatingconnected to at least a portion of a substrate, wherein the at leastpartial coating is adapted to switch from a first state to a secondstate in response to at least actinic radiation, to revert back to thefirst state in response to thermal energy, and to linearly polarize atleast transmitted radiation in at least one of the first state and thesecond state. Further, according to various non-limiting embodiments,the at least partial coating can comprise at least onephotochromic-dichroic compound that is at least partially aligned.

Additionally, according to various non-limiting embodiments disclosedherein, the at least partial coating having the first state and thesecond state can further comprise at least one additive that mayfacilitate one or more of the processing, the properties, or theperformance of the at least partial coating. Non-limiting examples ofsuch additives include dyes, alignment promoters, kinetic enhancingadditives, photoinitiators, thermal initiators, polymerizationinhibitors, solvents, light stabilizers (such as, but not limited to,ultraviolet light absorbers and light stabilizers, such as hinderedamine light stabilizers (HALS)), heat stabilizers, mold release agents,rheology control agents, leveling agents (such as, but not limited to,surfactants), free radical scavengers, and adhesion promoters (such ashexanediol diacrylate and coupling agents).

Non-limiting examples of dyes that can be present in the at leastpartial coating according to various non-limiting embodiments disclosedherein include organic dyes that are capable of imparting a desiredcolor or other optical property to the at least partial coating.

As used herein, the term “alignment promoter” means an additive that canfacilitate at least one of the rate and uniformity of the alignment of amaterial to which it is added. Non-limiting examples of alignmentpromoters that can be present in the at least partial coatings accordingto various non-limiting embodiments disclosed herein include thosedescribed in U.S. Pat. No. 6,338,808 and U.S. Patent Publication No.2002/0039627, which are hereby specifically incorporated by referenceherein.

Non-limiting examples of kinetic enhancing additives that can be presentin the at least partial coating according to various non-limitingembodiments disclosed herein include epoxy-containing compounds, organicpolyols, and/or plasticizers. More specific examples of such kineticenhancing additives are disclosed in U.S. Pat. No. 6,433,043 and U.S.Patent Publication No. 2003/0045612, which are hereby specificallyincorporated by reference herein.

Non-limiting examples of photoinitiators that can be present in the atleast partial coating according to various non-limiting embodimentsdisclosed herein include cleavage-type photoinitiators andabstraction-type photoinitiators. Non-limiting examples of cleavage-typephotoinitiators include acetophenones, α-aminoalkylphenones, benzoinethers, benzoyl oximes, acylphosphine oxides and bisacylphosphine oxidesor mixtures of such initiators. A commercial example of such aphotoinitiator is DAROCURE® 4265, which is available from CibaChemicals, Inc. Non-limiting examples of abstraction-typephotoinitiators include benzophenone, Michler's ketone, thioxanthone,anthraquinone, camphorquinone, fluorone, ketocoumarin or mixtures ofsuch initiators.

Another non-limiting example of a photoinitiator that can be present inthe at least partial coating according to various non-limitingembodiments disclosed herein is a visible light photoinitiator.Non-limiting examples of suitable visible light photoinitiators are setforth at column 12, line 11 to column 13, line 21 of U.S. Pat. No.6,602,603, which is specifically incorporated by reference herein.

Non-limiting examples of thermal initiators include organic peroxycompounds and azobis(organonitrile) compounds. Specific non-limitingexamples of organic peroxy compounds that are useful as thermalinitiators include peroxymonocarbonate esters, such astertiarybutylperoxy isopropyl carbonate; peroxydicarbonate esters, suchas di(2-ethylhexyl)peroxydicarbonate, di(secondarybutyl)peroxydicarbonate and diisopropylperoxydicarbonate;diacyperoxides, such as 2,4-dichlorobenzoyl peroxide, isobutyrylperoxide, decanoyl peroxide, lauroyl peroxide, propionyl peroxide,acetyl peroxide, benzoyl peroxide and p-chlorobenzoyl peroxide;peroxyesters such as t-butylperoxy pivalate, t-butylperoxy octylate andt-butylperoxyisobutyrate; methylethylketone peroxide, andacetylcyclohexane sulfonyl peroxide. In one non-limiting embodiment thethermal initiators used are those that do not discolor the resultingpolymerizate. Non-limiting examples of azobis(organonitrile) compoundsthat can be used as thermal initiators include azobis(isobutyronitrile),azobis(2,4-dimethylvaleronitrile) or a mixture thereof.

Non-limiting examples of polymerization inhibitors include:nitrobenzene, 1,3,5,-trinitrobenzene, p-benzoquinone, chloranil, DPPH,FeCl₃, CuCl₂, oxygen, sulfur, aniline, phenol, p-dihydroxybenzene,1,2,3-trihydroxybenzene, and 2,4,6-trimethylphenol.

Non-limiting examples of solvents that can be present in the at leastpartial coating according to various non-limiting embodiments disclosedherein include those that will dissolve solid components of the coating,that are compatible with the coating and the elements and substrates,and/or can ensure uniform coverage of the exterior surface(s) to whichthe coating is applied. Potential solvents include, but are not limitedto, the following: propylene glycol monomethyl ether acetate and theirderivates (sold as DOWANOL® industrial solvents), acetone, amylpropionate, anisole, benzene, butyl acetate, cyclohexane, dialkyl ethersof ethylene glycol, e.g., diethylene glycol dimethyl ether and theirderivates (sold as CELLOSOLVE® industrial solvents), diethylene glycoldibenzoate, dimethyl sulfoxide, dimethyl formamide, dimethoxybenzene,ethyl acetate, isopropyl alcohol, methyl cyclohexanone, cyclopentanone,methyl ethyl ketone, methyl isobutyl ketone, methyl propionate,propylene carbonate, tetrahydrofuran, toluene, xylene, 2-methoxyethylether, 3-propylene glycol methyl ether, and mixtures thereof.

In another non-limiting embodiment, the at least partial coating havingthe first state and the second state can further comprise at least oneconventional dichroic compound. Non-limiting examples of suitableconventional dichroic compounds include azomethines, indigoids,thioindigoids, merocyanines, indans, quinophthalonic dyes, perylenes,phthaloperines, triphenodioxazines, indoloquinoxalines,imidazo-triazines, tetrazines, azo and (poly)azo dyes, benzoquinones,naphthoquinones, anthroquinone and (poly)anthroquinones,anthropyrimidinones, iodine and iodates. In another non-limitingembodiment, the dichroic material can be a polymerizable dichroiccompound. That is, according to this non-limiting embodiment, thedichroic material can comprise at least one group that is capable ofbeing polymerized (i.e., a “polymerizable group”). For example, althoughnot limiting herein, in one non-limiting embodiment the at least onedichroic compound can have at least one alkoxy, polyalkoxy, alkyl, orpolyalkyl substituent terminated with at least one polymerizable group.

Still further, the at least partial coating having the first state andthe second state adapted can comprise at least one conventionalphotochromic compound. As used herein, the term “conventionalphotochromic compound” includes both thermally reversible andnon-thermally reversible (or photo-reversible) photochromic compounds.Generally, although not limiting herein, when two or more conventionalphotochromic materials are used in combination with each other or with aphotochromic-dichroic compound, the various materials can be chosen tocomplement one another to produce a desired color or hue. For example,mixtures of photochromic compounds can be used according to certainnon-limiting embodiments disclosed herein to attain certain activatedcolors, such as a near neutral gray or near neutral brown. See, forexample, U.S. Pat. 5,645,767, column 12, line 66 to column 13, line 19,the disclosure of which is specifically incorporated by referenceherein, which describes the parameters that define neutral gray andbrown colors.

The optical elements according to various non-limiting embodimentsdisclosed herein can further comprise at least one additional at leastpartial coating that can facilitate bonding, adhering, or wetting of anyof the various coatings connected to the substrate of the opticalelement. For example, according to one non-limiting embodiment, theoptical element can comprise an at least partial primer coating betweenthe at least partial coating having the first state and the second stateand a portion of the substrate. Further, in some non-limitingembodiments disclosed herein, the primer coating can serve as a barriercoating to prevent interaction of the coating ingredients with theelement or substrate surface and vice versa.

Non-limiting examples of primer coatings that can be used in conjunctionwith various non-limiting embodiments disclosed herein include coatingscomprising coupling agents, at least partial hydrolysates of couplingagents, and mixtures thereof. As used herein “coupling agent” means amaterial having at least one group capable of reacting, binding and/orassociating with a group on at least one surface. In one non-limitingembodiment, a coupling agent can serve as a molecular bridge at theinterface of at least two surfaces that can be similar or dissimilarsurfaces. Coupling agents, in another non-limiting embodiment, can bemonomers, oligomers, pre-polymers and/or polymers. Such materialsinclude, but are not limited to, organo-metallics such as silanes,titanates, zirconates, aluminates, zirconium aluminates, hydrolysatesthereof and mixtures thereof. As used herein the phrase “at leastpartial hydrolysates of coupling agents” means that at least some to allof the hydrolyzable groups on the coupling agent are hydrolyzed. Inaddition to coupling agents and/or hydrolysates of coupling agents, theprimer coatings can comprise other adhesion enhancing ingredients. Forexample, although not limiting herein, the primer coating can furthercomprise an adhesion-enhancing amount of an epoxy-containing material.Adhesion-enhancing amounts of an epoxy-containing materials when addedto the coupling agent containing coating composition can improve theadhesion of a subsequently applied coating as compared to a couplingagent containing coating composition that is essentially free of theepoxy-containing material. Other non-limiting examples of primercoatings that are suitable for use in conjunction with the variousnon-limiting embodiments disclosed herein include those described U.S.Pat. No. 6,602,603 and U.S. Pat. No. 6,150,430, which are herebyspecifically incorporated by reference.

The optical elements according to various non-limiting embodimentsdisclosed herein can further comprise at least one additional at leastpartial coating chosen from conventional photochromic coatings,anti-reflective coatings, linearly polarizing coatings, circularlypolarizing coatings, elliptically polarizing coatings, transitionalcoatings, primer coatings (such as those discussed above), andprotective coatings connected to at least a portion of the substrate.For example, although not limiting herein, the at least one additionalat least partial coating can be over at least a portion of the at leastpartial coating having the first state and the second state, i.e., as anovercoating; or under at least a portion of the at least partialcoating, i.e., as an undercoating. Additionally or alternatively, the atleast partial coating having the first state and the second state can beconnected at least a portion of a first surface of the substrate and theat least one additional at least partial coating can be connected to atleast a portion of a second surface of the substrate, wherein the firstsurface is opposite the second surface.

Non-limiting examples of conventional photochromic coatings includecoatings comprising any of the conventional photochromic compounds thatare discussed in detail below. For example, although not limitingherein, the photochromic coatings can be photochromic polyurethanecoatings, such as those described in U.S. Pat. No. 6,187,444;photochromic aminoplast resin coatings, such as those described in U.S.Pat. Nos. 4,756,973, 6,432,544 and 6,506,488; photochromic polysilanecoatings, such as those described in U.S. Pat. No. 4,556,605;photochromic poly(meth)acrylate coatings, such as those described inU.S. Pat. Nos. 6,602,603, 6,150,430 and 6,025,026, and WIPO PublicationWO 01/02449; polyanhydride photochromic coatings, such as thosedescribed in U.S. Pat. No. 6,436,525; photochromic polyacrylamidecoatings such as those described in U.S. Pat. No. 6,060,001;photochromic epoxy resin coatings, such as those described in U.S. Pat.Nos. 4,756,973 and 6,268,055; and photochromic poly(urea-urethane)coatings, such as those described in U.S. Pat. No. 6,531,076. Thespecifications of the aforementioned U.S. Patents and internationalpublications are hereby specifically incorporated by reference herein.

Non-limiting examples of linearly polarizing coatings include, but arenot limited to, coatings comprising conventional dichroic compounds suchas, but not limited to, those discussed above.

As used herein the term “transitional coating” means a coating that aidsin creating a gradient in properties between two coatings. For example,although not limiting herein, a transitional coating can aid in creatinga gradient in hardness between a relatively hard coating and arelatively soft coating. Non-limiting examples of transitional coatingsinclude radiation-cured acrylate-based thin films.

Non-limiting examples of protective coatings include abrasion-resistantcoatings comprising organo silanes, abrasion-resistant coatingscomprising radiation-cured acrylate-based thin films, abrasion-resistantcoatings based on inorganic materials such as silica, titania and/orzirconia, organic abrasion-resistant coatings of the type that areultraviolet light curable, oxygen barrier-coatings, UV-shieldingcoatings, and combinations thereof. For example, according to onenon-limiting embodiment, the protective coating can comprise a firstcoating of a radiation-cured acrylate-based thin film and a secondcoating comprising an organo-silane. Non-limiting examples of commercialprotective coatings products include SILVUE® 124 and HI-GARD® coatings,available from SDC Coatings, Inc. and PPG Industries, Inc.,respectively.

Other non-limiting embodiments disclosed herein provide an opticalelement comprising a substrate and at least one at least partiallyaligned photochromic-dichroic compound connected to at least a portionthe substrate and having an average absorption ratio greater than 2.3 inan activated state as determined according to the CELL METHOD. Further,according to various non-limiting embodiments disclosed herein, theabsorption ratio of the at least partially aligned photochromic-dichroiccompound can range from 4 to 20, can further range from 3 to 30, and canstill further range from 2.5 to 50 or greater.

As previously discussed, the term “connected to” means in direct contactwith an object or indirect contact with an object through one or moreother structures, at least one of which is in direct contact with theobject. Thus, according to the above-mentioned non-limiting embodiments,the at least one at least partially aligned photochromic-dichroiccompound can be connected to the at least a portion of the substrate canbe in direct contact with the at least a portion of the substrate, or itcan be in contact with one or more other structures or materials thatare in direct or indirect contact with the substrate. For example,although not limiting herein, in one non-limiting embodiment, the atleast one at least partially aligned photochromic-dichroic compound canbe present as part of an at least partial coating or polymeric sheetthat is in direct contact with the at least a portion of the substrate.In another non-limiting embodiment, the least one at least partiallyaligned photochromic-dichroic compound can be present as part of acoating or a sheet that is in direct contact with one or more other atleast partial coatings or sheets, at least one of which is in directcontact with the at least a portion of the substrate.

According to still other non-limiting embodiments, the at least one atleast partially aligned photochromic-dichroic compound can be containedin an at least partially ordered liquid crystal material that is indirect (or indirect) contact with at least a portion the substrate.Further, according to this non-limiting embodiment, the optical elementcan comprise two substrates and the at least partially ordered liquidcrystal material containing the at least partially alignedphotochromic-dichroic compound can be positioned between the twosubstrates, for example, to form an active or a passive liquid crystalcell.

Non-limiting examples of photochromic-dichroic compounds suitable forused in conjunction with various non-limiting embodiments disclosedherein include:

-   (1)    3-phenyl-3-(4-(4-(3-piperidin-4-yl-propyl)piperidino)phenyl)-13,13-dimethyl-indeno[2′,3′:3,4]-naphtho[1,2-b]pyran;-   (2)    3-phenyl-3-(4-(4-(3-(1-(2-hydroxyethyl)piperidin-4-yl)propyl)piperidino)phenyl)-13,13-dimethyl-indeno[2′,3′:3,4]naphtho[1,2-b]pyran;-   (3) 3-phenyl-3-(4-(4-(4-butyl-phenylcarbamoyl)-piperidin-1-yl)    phenyl)-13,13-dimethyl-6-methoxy-7-(4-phenyl-piperazin-1-yl)indeno[2′,3′:3,4]naphtho[1,2-b]pyran;-   (4)    3-phenyl-3-(4-([1,4′]bipiperidinyl-1′-yl)phenyl)-13,13-dimethyl-6-methoxy-7-([1,4′]bipiperidinyl-1′-yl)indeno[2′,3′:3,4]naphtho[1,2-b]pyran;-   (5)    3-phenyl-3-(4-(4-phenyl-piperazin-1-yl)phenyl)-13,13-dimethyl-6-methoxy-7-(4-(4-hexylbenzoyloxy)-piperidin-1-yl)indeno[2′,3′:3,4]naphtho[1,2-b]pyran;-   (6)    3-phenyl-3-(4-(4-phenyl-piperazin-1-yl)phenyl)-13,13-dimethyl-6-methoxy-7-(4-(4′-octyloxy-biphenyl-4-carbonyloxy)-piperidin-1-yl)indeno[2′,3′:3,4]naphtho[1,2-b]pyran;-   (7)    3-phenyl-3-(4-(4-phenyl-piperazin-1-yl)phenyl)-13,13-dimethyl-6-methoxy-7-{4-[17-(1,5-dimethyl-hexyl)-10,13-dimethyl-2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthren-3-yloxycarbonyloxy]-piperidin-1-yl}-indeno[2′,3′:3,4]naphtho[1,2-b]pyran;-   (8)    3-phenyl-3-(4-{4-[17-(1,5-dimethyl-hexyl)-10,13-dimethyl-2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthren-3-yloxycarbonyloxy]-piperidin-1-yl}-phenyl)-13,13-dimethyl-6-methoxy-7-{4-[17-(1,5-dimethyl-hexyl)-10,13-dimethyl-2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthren-3-yloxycarbonyloxy]-piperidin-1-yl}-)indeno[2′,3′:3,4]naphtho[1,2-b]pyran;-   (9)    3-phenyl-3-(4-(4-phenylpiperazin-1-yl)phenyl)-13,13-dimethyl-6-methoxy-7-(4-(4-(4′-octyloxy-biphenyl-4-carbonyloxy)phenyl)piperazin-1-yl)indeno[2′,3′:3,4]naphtho[1,2-b]pyran;-   (10)    3-phenyl-3-(4-(4-phenyl-piperazin-1-yl)phenyl)-13,13-dimethyl-6-methoxy-7-(4-(4-(4-hexyloxyphenylcarbonyloxy)phenyl)piperazin-1-yl)indeno[2′,3′:3,4]naphtho[1,2-b]pyran;-   (11)    3-phenyl-3-(4-(4-phenyl-piperazin-1-yl)phenyl)-13,13-dimethyl-6-methoxy-7-(4-(4-(4-(2-fluorobenzoyloxy)benzoyloxy)phenyl)piperazin-1-yl)indeno[2′,3′:3,4]naphtho[1,2-b]pyran;-   (12)    3-phenyl-3-(4-(pyrrolidin-1-yl)phenyl)-13-hydroxy-13-ethyl-6-methoxy-7-(4-(4-(4-hexylbenzoyloxy)phenyl)piperazin-1-yl)indeno[2′,3′:3,4]naphtho[1,2-b]pyran;-   (13)    3-phenyl-3-(4-(pyrrolidin-1-yl)phenyl)-13,13-dimethyl-6-methoxy-7-(4-(4-hexylbenzoyloxy)benzoyloxy)-indeno[2′,3′:3,4]naphtho[1,2-b]pyran;-   (14)    3-phenyl-3-(4-(pyrrolidin-1-yl)phenyl)-13,13-dimethyl-6-methoxy-7-(4-(4-(4-hexylbenzoyloxy)benzoyloxy)benzoyloxy)indeno[2′,3′:3,4]naphtho[1,2-b]pyran;-   (15)    3-phenyl-3-(4-(4-methoxyphenyl)-piperazin-1-yl))phenyl)-13,13-dimethyl-6-methoxy-7-(4-(4-(3-phenylprop-2-ynoyloxy)phenyl)piperazin-1-yl)-indeno[2′,3′:3,4]naphtho[1,2-b]pyran;-   (16)    3-(4-methoxyphenyl)-3-(4-(4-methoxyphenyl)piperazin-1-yl)phenyl)-13-ethyl-13-hydroxy-6-methoxy-7-(4-(4-(4-hexylbenzoyloxy)phenyl)piperazin-1-yl)indeno[2′,3′:3,4]naphtho[1,2-b]pyran;-   (17)    3-phenyl-3-{4-(pyrrolidin-1-yl)phenyl)-13-[17-(1,5-dimethyl-hexyl)-10,13-dimethyl-2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthren-3-yloxy]-13-ethyl-6-methoxy-7-(4-[17-(1,5-dimethyl-hexyl)-10,13-dimethyl-2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthren-3-yloxycarbonyloxy]-piperadin-1-yl)-indeno[2′,3′:3,4]naphtho[1,2-b]pyran;-   (18)    3-phenyl-3-(4-{4-[17-(1,5-dimethyl-hexyl)-10,13-dimethyl-2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthren-3-yloxycarbonyloxy]-piperidin-1-yl}-phenyl)-13-ethyl-13-hydroxy-6-methoxy-7-{4-[17-(1,5-dimethyl-hexyl)-10,13-dimethyl-2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthren-3-yloxycarbonyloxy]-piperidin-1-yl}-)indeno[2′,3′:3,4]naphtho[1,2-b]pyran;-   (19)    3-phenyl-3-{4-(pyrrolidin-1-yl)phenyl)-13,13-dimethyl-6-methoxy-7-(4-(4-(4-(3-phenyl-3-{4-(pyrrolidin-1-yl)phenyl}-13,13-dimethyl-6-methoxy-indeno[2′,3′:3,4]naphtho[1,2-b]pyran-7-yl)-piperadin-1-yl)oxycarbonyl)phenyl)phenyl)cabonyloxy)-indeno[2′,3′:3,4]naphtho[1,2-b]pyran;-   (20)    3-{4-[4-(4-methoxy-phenyl)-piperazin-1-yl]-phenyl}-3-phenyl-7-methoxycarbonyl-3H-naphtho[2,1-b]pyran;-   (21)    3-{4-[4-(4-methoxy-phenyl)-piperazin-1-yl]-phenyl}-3-phenyl-7-hydroxycarbonyl-3H-naphtho[2,1-b]pyran;-   (22)    3-{4-[4-(4-methoxy-phenyl)-piperazin-1-yl]-phenyl}-3-phenyl-7-(4-phenyl-(phen-1-oxy)carbonyl)-3H-naphtho[2,1-b]pyran;-   (23)    3-{4-[4-(4-methoxy-phenyl)-piperazin-1-yl]-phenyl}-3-phenyl-7-(N-(4-((4-dimethylamino)phenyl)diazenyl)phenyl)carbamoyl-3H-naphtho[2,1-b]pyran;-   (24)    2-phenyl-2-{4-[4-(4-methoxy-phenyl)-piperazin-1-yl]-phenyl}-benzofuro[3′,2′:7,8]benzo[b]pyran;-   (25)    2-phenyl-2-{4-[4-(4-methoxy-phenyl)-piperazin-1-yl]-phenyl}-benzothieno[3′,2′:7,8]benzo[b]pyran;-   (26)    7-{17-(1,5-dimethyl-hexyl)-10,13-dimethyl-2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthren-3-yloxycarbonyloxy}-2-phenyl-2-(4-pyrrolidin-1-yl-phenyl)-6-methoxycarbonyl-2H-benzo[b]pyran;-   (27)    2-phenyl-2-{4-[4-(4-methoxy-phenyl)-piperazin-1-yl]-phenyl}-9-hydroxy-8-methoxycarbonyl-2H-naphtho[1,2-b]pyran;-   (28)    2-phenyl-2-{4-[4-(4-methoxy-phenyl)-piperazin-1-yl]-phenyl}-9-hydroxy-8-(N-(4-butyl-phenyl))carbamoyl-2H-naphtho[1,2-b]pyran;-   (29)    2-phenyl-2-{4-[4-(4-methoxy-phenyl)-piperazin-1-yl]-phenyl}-9-hydroxy-8-(N-(4-phenyl)phenyl)carbamoyl-2H-naphtho[1,2-b]pyran;-   (30)    1,3,3-trimethyl-6′-(4-ethoxycarbonyl)-piperidin-1-yl)-spiro[indoline-2,3′-3H-naphtho[2,1-b][1,4]oxazine];-   (31)    1,3,3-trimethyl-6′-(4-[N-(4-butylphenyl)carbamoyl]-piperidin-1-yl)-spiro[indoline-2,3′-3H-naphtho[2,1-b][1,4]oxazine];-   (32)    1,3,3-trimethyl-6′-(4-(4-methoxyphenyl)piperazin-1-yl)-spiro[indoline-2,3′-3H-naphtho[2,1-b][1,4]oxazine];-   (33)    1,3,3-trimethyl-6′-(4-(4-hydroxyphenyl)piperazin-1-yl)-spiro[indoline-2,3′-3H-naphtho[2,1-b][1,4]oxazine];-   (34)    1,3,3,5,6-pentamethyl-7′-(4-(4-methoxyphenyl)piperazin-1-yl)-spiro[indoline-2,3′-3H-naphtho[2,1-b][1,4]oxazine];-   (35)    1,3-diethyl-3-methyl-5-methoxy-6′-(4-(4′-Hexyloxy-biphenyl-4-carbonyloxy)-piperidin-1-yl)-spiro[indoline-2,3′-3H-naphtho[2,1-b][1,4]oxazine];-   (36)    1,3-diethyl-3-methyl-5-[4-(4-pentadecafluoroheptyloxy-phenylcarbamoyl)-benzyloxy]-6′-(4-(4′-hexyloxy-biphenyl-4-carbonyloxy)-piperidin-1-yl)-spiro[indoline-2,3′-3H-naphtho[2,1-b][1,4]oxazine];-   (37)    2-phenyl-2-{4-[4-(4-methoxy-phenyl)-piperazin-1-yl]-phenyl}-5-carbomethoxy-8-(N-(4-phenyl)phenyl)carbamoyl-2H-naphtho[1,2-b]pyran;-   (38)    2-phenyl-2-{4-[4-(4-methoxy-phenyl)-piperazin-1-yl]-phenyl}-5-carbomethoxy-8-(N-4-phenyl)phenyl)carbamoyl-2H-fluoantheno[1,2-b]pyran;-   (39)    2-phenyl-2-{4-[4-(4-methoxy-phenyl)-piperazin-1-yl]-phenyl}-5-carbomethoxy-11-(4-{17-(1,5-dimethyl-hexyl)-10,13-dimethyl-2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthren-3-yloxycarbonyloxy}phenyl)-2H-fluoantheno[1,2-b]pyran;-   (40)    1-(4-carboxybutyl)-6-(4-(4-propylphenyl)carbonyloxy)phenyl)-3,3-dimethyl-6′-(4-ethoxycarbonyl)-piperidin-1-yl)-spiro[(1,2-dihydro-9H-dioxolano[4′,5′:6,7]indoline-2,3′-3H-naphtho[2,1-b][1,4]oxazine];-   (41)    1-(4-carboxybutyl)-6-(4-(4-propylphenyl)carbonyloxy)phenyl)-3,3-dimethyl-7′-(4-ethoxycarbonyl)-piperidin-1-yl)-spiro[(1,2-dihydro-9H-dioxolano[4′,5′:6,7]indoline-2,3′-3H-naphtho[1,2-b][1,4]oxazine];-   (42)    1,3-diethyl-3-methyl-5-(4-{17-(1,5-dimethyl-hexyl)-10,13-dimethyl-2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthren-3-yloxycarbonyloxy}phenyl)-6′-(4-(4′-hexyloxy-biphenyl-4-carbonyloxy)-piperidin-1-yl)-spiro[indoline-2,3′-3H-naphtho[2,1-b][1,4]oxazine];-   (43)    1-butyl-3-ethyl-3-methyl-5-methoxy-7′-(4-(4′-Hexyloxy-biphenyl-4-carbonyloxy)-piperidin-1-yl)-spiro[indoline-2,3′-3H-naphtho[1,2-b][1,4]oxazine];-   (44)    2-phenyl-2-{4-[4-(4-methoxy-phenyl)-piperazin-1-yl]-phenyl}-5-methoxycarbonyl-6-methyl-2H-9-(4-(4-propylphenyl)carbonyloxy)phenyl)(1,2-dihydro-9H-dioxolano[4′,5′:6,7]naphtho[1,2-b]pyran;-   (45)    3-(4-methoxyphenyl)-3-(4-(4-methoxyphenyl)piperazin-1-yl)phenyl)-13-ethyl-13-hydroxy-6-methoxy-7-(4-(4-propylphenyl)carbonyloxy)phenyl)-[1,2-dihydro-9H-dioxolano[4″,5″:6,7][indeno[2′,3′:3,4]]naphtho[1,2-b]pyran;-   (46)    3-phenyl-3-(4-(4-methoxyphenyl)piperazin-1-yl)phenyl)-13-ethyl-13-hydroxy-6-methoxy-7-(4-(4-hexylphenyl)carbonyloxy)phenyl)-[1,2-dihydro-9H-dioxolano[4″,5″:5,6][indeno[2′,3′:3,4]]naphtho[1,2-b]pyran;-   (47)    4-(4-((4-cyclohexylidene-1-ethyl-2,5-dioxopyrrolin-3-ylidene)ethyl)-2-thienyl)phenyl-(4-propyl)benzoate;-   (48)    4-(4-((4-adamantan-2-ylidene-1-(4-(4-hexylphenyl)carbonyloxy)phenyl)-2,5-dioxopyrrolin-3-ylidene)ethyl)-2-thienyl)phenyl-(4-propyl)benzoate;-   (49)    4-(4-((4-adamantan-2-ylidene-2,5-dioxo-1-(4-(4-(4-propylphenyl)piperazinyl)phenyl)pyrrolin-3-ylidene)ethyl)-2-thienyl)phenyl    (4-propyl)benzoate;-   (50)    4-(4-((4-adamantan-2-ylidene-2,5-dioxo-1-(4-(4-(4-propylphenyl)piperazinyl)phenyl)pyrrolin-3-ylidene)ethyl)-1-methylpyrrol-2-yl)phenyl    (4-propyl)benzoate;-   (51)    4-(4-((4-adamantan-2-ylidene-2,5-dioxo-1-(4-{17-(1,5-dimethyl-hexyl)-10,13-dimethyl-2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthren-3-yloxycarbonyloxy}phenyl)pyrrolin-3-ylidene)ethyl)-1-methylpyrrol-2-yl)phenyl    (4-propyl)benzoate;-   (52)    4-(4-methyl-5,7-dioxo-6-(4-(4-(4-propylphenyl)piperazinyl)phenyl)spiro[8,7a-dihydrothiapheno[4,5-f]isoindole-8,2′-adamentane]-2-yl)phenyl(4-propyl)phenyl    benzoate;-   (53)    N-(4-{17-(1,5-dimethyl-hexyl)-10,13-dimethyl-2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthren-3-yloxycarbonyloxy}phenyl-6,7-dihydro-4-methyl-2-phenylspiro(5,6-benzo[b]thiophenedicarboxyimide-7,2-tricyclo[3.3.1.1]decane);-   (54)    N-cyanomethyl-6,7-dihydro-2-(4-(4-(4-propylphenyl)piperazinyl)phenyl)-4-methylspiro(5,6-benzo[b]thiophenedicarboxyimide-7,2-tricyclo[3.3.1.1]decane);-   (55)    N-phenylethyl-6,7-dihydro-2-(4-(4-(4-hexylbenzoyloxy)phenyl)piperazin-1-yl)phenyl-4-methylspiro(5,6-benzo[b]thiophenedicarboxyimide-7,2-tricyclo[3.3.1.1]decane);-   (56)    N-phenylethyl-6,7-dihydro-2-(4-(4-(4-hexylbenzoyloxy)phenyl)piperazin-1-yl)phenyl-4-cyclopropyl    spiro(5,6-benzo[b]thiophenedicarboxyimide-7,2-tricyclo[3.3.1.1]decane);-   (57)    N-phenylethyl-6,7-dihydro-2-(4-(4-(4-hexylbenzoyloxy)phenyl)piperazin-1-yl)phenyl-4-cyclopropyl    spiro(5,6-benzo[b]furodicarboxyimide-7,2-tricyclo[3.3.1.1]decane);-   (58)    N-cyanomethyl-6,7-dihydro-4-(4-(4-(4-hexylbenzoyloxy)phenyl)piperazin-1-yl)phenyl-2-phenylspiro(5,6-benzo[b]thiophenedicarboxyimide-7,2-tricyclo[3.3.1.1]decane);-   (59)    N-[17-(1,5-dimethyl-hexyl)-10,13-dimethyl-2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthren-3-yloxycarbonyl-6,7-dihydro-2-(4-methoxyphenyl)phenyl-4-methylspiro(5,6-benzo[b]thiophenedicarboxyimide-7,2-tricyclo[3.3.1.1]decane);-   (60)    N-cyanomethyl-2-(4-(6-(4-butylphenyl)carbonyloxy-(4,8-dioxabicyclo[3.3.0]oct-2-yl))oxycarbonyl)phenyl-6,7-dihydro-4-cyclopropylspiro(5,6-benzo[b]thiophenedicarboxyimide-7,2-tricyclo[3.3.1.1]decane);-   (61)    6,7-dihydro-N-methoxycarbonylmethyl-4-(4-(6-(4-butylphenyl)carbonyloxy-(4,8-dioxabicyclo[3.3.0]oct-2-yl))oxycarbonyl)phenyl-2-phenylspiro(5,6-benzo[b]thiophenedicarboxyimide-7,2-tricyclo[3.3.1.1]decane);    and-   (62)    3-phenyl-3-(4-pyrrolidinylphenyl)-13,13-dimethyl-6-methoxy-7-(4-(4-(4-(4-(6-(4-(4-(4-nonylphenylcabonyloxy)phenyl)oxycarbonyl)phenoxy)hexyloxy)phenyl)piperazin-1-yl)indeno[2′,3′:3,4]naphtho[1,2-b]pyran.

More generally, such photochromic-dichroic compounds comprise: (a) atleast one photochromic group (PC) chosen from pyrans, oxazines, andfulgides; and (b) at least one lengthening agent attached to the atleast one photochromic group, wherein the lengthening agent (L) isrepresented by the following Formula I (which is described in detailbelow):—[S₁]_(c)-[Q₁-[S₂]_(d)]_(d)′-[Q₂-[S₃]_(e)]_(e′)-[Q₃-[S₄]_(f)]_(f′)—S₅—P  I

As used herein, the term “attached” means directly bonded to orindirectly bonded to through another group. Thus, for example, accordingto various non-limiting embodiments disclosed herein, L can be directlybonded to PC as a substituent on PC, or L can be a substituent onanother group (such as a group represented by R¹, which is discussedbelow) that is directly bonded to PC (i.e., L is indirectly bonded toPC). Although not limiting herein, according to various non-limitingembodiments, L can be attached to PC so as to extend or lengthen PC inan activated state such that the absorption ratio of the extended PC(i.e., the photochromic compound) is enhanced as compared to PC alone.Although not limiting herein, according to various non-limitingembodiments, the location of attachment of L on PC can be chosen suchthat L lengthens PC in at least one of a direction parallel to and adirection perpendicular to a theoretical transitional dipole moment ofthe activated form of PC. As used herein the term “theoreticaltransitional dipole moment” refers to transient dipolar polarizationcreated by interaction of electromagnetic radiation with the molecule.See, for example, IUPAC Compendium of Chemical Technology, 2^(nd) Ed.,International Union of Pure and Applied Chemistry (1997).

With reference to Formula I above, each Q₁, Q₂, and Q₃ can beindependently chosen for each occurrence from: a divalent group chosenfrom an unsubstituted or a substituted aromatic group, an unsubstitutedor a substituted alicyclic group, an unsubstituted or a substitutedheterocyclic group, and mixtures thereof, wherein substituents arechosen from: a group represented by P (as set forth below), aryl, thiol,amide, liquid crystal mesogens, halogen, C₁-C₁₈ alkoxy, poly(C₁-C₁₈alkoxy), amino, amino(C₁-C₁₈)alkylene, C₁-C₁₈alkylamino,di-(C₁-C₁₈)alkylamino, C₁-C₁₈ alkyl, C₂-C₁₈ alkene, C₂-C₁₈ alkyne,C₁-C₁₈ alkyl(C₁-C₁₈)alkoxy, C₁-C₁₈ alkoxycarbonyl, C₁-C₁₈ alkylcarbonyl,C₁-C₁₈ alkyl carbonate, aryl carbonate, C₁-C₁₈acetyl, C₃-C₁₀cycloalkyl,C₃-C₁₀cycloalkoxy, isocyanato, amido, cyano, nitro, a straight-chain orbranched C₁-C₁₈ alkyl group that is mono-substituted with cyano, halo,or C₁-C₁₈ alkoxy, or poly-substituted with halo, and a group representedby one of the following formulae: —M(T)_((t-1)) and —M(OT)_((t-1)),wherein M is chosen from aluminum, antimony, tantalum, titanium,zirconium and silicon, T is chosen from organofunctional radicals,organofunctional hydrocarbon radicals, aliphatic hydrocarbon radicalsand aromatic hydrocarbon radicals, and t is the valence of M. As usedherein, the prefix “poly” means at least two.

As discussed above, Q₁, Q₂, and Q₃ can be independently chosen for eachoccurrence from a divalent group, such as an unsubstituted or asubstituted aromatic group, unsubstituted or substituted heterocyclicgroup, and an unsubstituted or substituted alicylic group. Non-limitingexamples of useful aromatic groups include: benzo, naphtho, phenanthro,biphenyl, tetrahydro naphtho, terphenyl, and anthraceno.

As used herein the term “heterocyclic group” means a compound having aring of atoms, wherein at least one atom forming the ring is differentthan the other atoms forming the ring. Further, as used herein, the termheterocyclic group specifically excludes fused heterocyclic groups.Non-limiting examples of suitable heterocyclic groups from which Q₁, Q₂,and Q₃ can be chosen include: isosorbitol, dibenzofuro, dibenzothieno,benzofuro, benzothieno, thieno, furo, dioxino, carbazolo, anthranilyl,azepinyl, benzoxazolyl, diazepinyl, dioazlyl, imidazolidinyl,imidazolyl, imidazolinyl, indazolyl, indoleninyl, indolinyl,indolizinyl, indolyl, indoxazinyl, isobenzazolyl, isoindolyl,isooxazolyl, isooxazyl, isopyrroyl, isoquinolyl, isothiazolyl,morpholino, morpholinyl, oxadiazolyl, oxathiazolyl, oxathiazyl,oxathiolyl, oxatriazolyl, oxazolyl, piperazinyl, piperazyl, piperidyl,purinyl, pyranopyrrolyl, pyrazinyl, pyrazolidinyl, pyrazolinyl,pyrazolyl, pyrazyl, pyridazinyl, pyridazyl, pyridyl, pyrimidinyl,pyrimidyl, pyridenyl, pyrrolidinyl, pyrrolinyl, pyrroyl, quinolizinyl,quinuclidinyl, quinolyl, thiazolyl, triazolyl, triazyl,N-arylpiperazino, aziridino, arylpiperidino, thiomorpholino,tetrahydroquinolino, tetrahydroisoquinolino, pyrryl, unsubstituted,mono- or di-substituted C₄-C₁₈ spirobicyclic amines, and unsubstituted,mono- or di-substituted C₄-C₁₈ spirotricyclic amines.

As discussed above, Q₁, Q₂, and Q₃ can be chosen from mono- ordi-substituted C₄-C₁₈ spirobicyclic amine and C₄-C₁₈ spirotricyclicamine. Non-limiting examples of suitable substituents include aryl,C₁-C₆ alkyl, C₁-C₆ alkoxy or phenyl (C₁-C₆ )alkyl. Specific non-limitingexamples of mono- or di-substituted spirobicyclic amines include:2-azabicyclo[2.2.1]hept-2-yl; 3-azabicyclo[3.2.1]oct-3-yl;2-azabicyclo[2.2.2]oct-2-yl; and 6-azabicyclo[3.2.2]nonan-6-yl. Specificnon-limiting examples of mono- or di-substituted tricyclic aminesinclude: 2-azatricyclo[3.3.1.1(3,7)]decan-2-yl;4-benzyl-2-azatricyclo[3.3.1.1 (3,7)]decan-2-yl;4-methoxy-6-methyl-2-azatricyclo[3.3.1.1(3,7)]decan-2-yl;4-azatricyclo[4.3.1.1(3,8)]undecan-4-yl; and7-methyl-4-azatricyclo[4.3.1.1(3,8)]undecan-4-yl. Examples of alicyclicgroups from which Q₁, Q₂, and Q₃ can be chosen include, withoutlimitation, cyclohexyl, cyclopropyl, norbornenyl, decalinyl,adamantanyl, bicycloctane, per-hydrofluorene, and cubanyl.

With continued reference to Formula I, and each S₁, S₂, S₃, S₄, and S₅is independently chosen for each occurrence from a spacer unit chosenfrom:

-   -   (1) —(CH₂)_(g)—, —(CF₂)_(h)—, —Si(CH₂)_(g)—,        —(Si[(CH₃)₂]O)_(h)—, wherein g is independently chosen for each        occurrence from 1 to 20; h is chosen from 1 to 16;    -   (2) —N(Z)-, —C(Z)=C(Z)-, —C(Z)=N—, —C(Z′)-C(Z′)-, wherein Z is        independently chosen for each occurrence from hydrogen, C₁-C₆        alkyl, cycloalkyl and aryl, and Z′ is independently chosen for        each occurrence from C₁-C₆ alkyl, cycloalkyl and aryl; and    -   (3) —O—, —C(O)—, —C—C—, —N═N—, —S—, —S(O)—, —S(O)(O)—,        straight-chain or branched C₁-C₂₄ alkylene residue, said C₁-C₂₄        alkylene residue being unsubstituted, mono-substituted by cyano        or halo, or poly-substituted by halo;        provided that when two spacer units comprising heteroatoms are        linked together the spacer units are linked so that heteroatoms        are not directly linked to each other and when S₁ and S₅ are        linked to PC and P, respectively, they are linked so that two        heteroatoms are not directly linked to each other. As used        herein the term “heteroatom” means atoms other than carbon or        hydrogen.

Further, in Formula I, according to various non-limiting embodiments, c,d, e, and f each can be independently chosen from an integer rangingfrom 1 to 20, inclusive; and d′, e′ and f′ each can be independentlychosen from 0, 1, 2, 3, and 4, provided that the sum of d′+e′+f′ is atleast 1. According to other non-limiting embodiments, c, d, e, and feach can be independently chosen from an integer ranging from 0 to 20,inclusive; and d′, e′ and f′ each can be independently chosen from 0, 1,2, 3, and 4, provided that the sum of d′+e′+f′ is at least 2. Accordingto still other non-limiting embodiments, c, d, e, and f each can beindependently chosen from an integer ranging from 0 to 20, inclusive;and d′, e′ and f′ each can be independently chosen from 0, 1, 2, 3, and4, provided that the sum of d′+e′+f′ is at least 3. According to stillother non-limiting embodiments, c, d, e, and f each can be independentlychosen from an integer ranging from 0 to 20, inclusive; and d′, e′ andf′ each can be independently chosen from 0, 1, 2, 3, and 4, providedthat the sum of d′+e′+f′ is at least 1.

Further, in Formula I, P can be chosen from: aziridinyl, hydrogen,hydroxy, aryl, alkyl, alkoxy, amino, alkylamino, alkylalkoxy,alkoxyalkoxy, nitro, polyalkyl ether,(C₁-C₆)alkyl(C₁-C₆)alkoxy(C₁-C₆)alkyl, polyethyleneoxy,polypropyleneoxy, ethylene, acrylate, methacrylate, 2-chloroacrylate,2-phenylacrylate, acryloylphenylene, acrylamide, methacrylamide,2-chloroacrylamide, 2-phenylacrylamide, epoxy, isocyanate, thiol,thioisocyanate, itaconic acid ester, vinyl ether, vinyl ester, a styrenederivative, siloxane, main-chain and side-chain liquid crystal polymers,a liquid crystal mesogen, ethyleneimine derivatives, maleic acidderivatives, fumaric acid derivatives, unsubstituted cinnamic acidderivatives, cinnamic acid derivatives that are substituted with atleast one of methyl, methoxy, cyano and halogen, and substituted andunsubstituted chiral and non-chiral monovalent or divalent groups chosenfrom steroid radicals, terpenoid radicals, alkaloid radicals andmixtures thereof, wherein the substituents are independently chosen froman alkyl, an alkoxy, amino, cycloalkyl, alkylalkoxy, a fluoroalkyl, acyanoalkyl, a cyanoalkoxy and mixtures thereof.

Further, although not limiting herein, when P is a polymerizable group,the polymerizable group can be any functional group adapted toparticipate in a polymerization reaction. Non-limiting examples ofpolymerization reactions include those described in the definition of“polymerization” in Hawley's Condensed Chemical Dictionary ThirteenthEdition, 1997, John Wiley & Sons, pages 901-902, which disclosure isincorporated herein by reference. For example, although not limitingherein, polymerization reactions include: “addition polymerization,” inwhich free radicals are the initiating agents that react with the doublebond of a monomer by adding to it on one side at the same time producinga new free electron on the other side; “condensation polymerization,” inwhich two reacting molecules combine to form a larger molecule withelimination of a small molecule, such as a water molecule; and“oxidative coupling polymerization.” Further, non-limiting examples ofpolymerizable groups include hydroxy, acryloxy, methacryloxy,2-(acryloxy)ethylcarbamyl, 2-(methacryloxy)ethylcarbamyl, isocyanate,aziridine, allylcarbonate, and epoxy, e.g., oxiranylmethyl.

Moreover, P can be chosen from a main-chain or a side-chain liquidcrystal polymer and a liquid crystal mesogen. As used herein, the termliquid crystal “mesogen” means rigid rod-like or disc-like liquidcrystal molecules. Further, as used herein the term “main-chain liquidcrystal polymer” refers to a polymer having liquid crystal mesogenswithin the backbone (i.e., the main chain) structure of the polymer. Asused herein the term “side-chain liquid crystal polymer” refers to apolymer having liquid crystal mesogens attached to the polymer at theside chains. Although not limiting herein, generally, the mesogens aremade up of two or more aromatic rings that restrict the movement of aliquid crystal polymer. Examples of suitable rod-like liquid crystalmesogens include without limitation: substituted or unsubstitutedaromatic esters, substituted or unsubstituted linear aromatic compounds,and substituted or unsubstituted terphenyls. According to anotherspecific, non-limiting embodiment, P can be chosen from a steroid, forexample and without limitation, a cholesterolic compound.

Non-limiting examples of thermally reversible photochromic pyrans fromwhich the photochromic group PC can be chosen include benzopyrans,naphthopyrans, e.g., naphtho[1,2-b]pyrans, naphtho[2,1-b]pyrans,indeno-fused naphthopyrans, such as those disclosed in U.S. Pat. No.5,645,767, and heterocyclic-fused naphthopyrans, such as those disclosedin U.S. Pat. Nos. 5,723,072, 5,698,141, 6,153,126, and 6,022,497, whichare hereby incorporated by reference; spiro-9-fluoreno[1,2-b]pyrans;phenanthropyrans; quinopyrans; fluoroanthenopyrans; spiropyrans, e.g.,spiro(benzindoline)naphthopyrans, spiro(indoline)benzopyrans,spiro(indoline)naphthopyrans, spiro(indoline)quinopyrans andspiro(indoline)pyrans. More specific examples of naphthopyrans and thecomplementary organic photochromic substances are described in U.S. Pat.No. 5,658,501, which are hereby specifically incorporated by referenceherein. Spiro(indoline)pyrans are also described in the text, Techniquesin Chemistry, Volume III, “Photochromism”, Chapter 3, Glenn H. Brown,Editor, John Wiley and Sons, Inc., New York, 1971, which is herebyincorporated by reference.

Non-limiting examples of photochromic oxazines from which PC can bechosen include benzoxazines, naphthoxazines, and spiro-oxazines, e.g.,spiro(indoline)naphthoxazines, spiro(indoline)pyridobenzoxazines,spiro(benzindoline)pyridobenzoxazines,spiro(benzindoline)naphthoxazines, spiro(indoline)benzoxazines,spiro(indoline)fluoranthenoxazine, and spiro(indoline)quinoxazine.Non-limiting examples of photochromic fulgides from which PC can bechosen include: fulgimides, and the 3-furyl and 3-thienyl fulgides andfulgimides, which are disclosed in U.S. Pat. No. 4,931,220 (which arehereby specifically incorporated by reference) and mixtures of any ofthe aforementioned photochromic materials/compounds.

Further, wherein the photochromic-dichroic compound comprises at leasttwo PCs, the PCs can be linked to one another via linking groupsubstituents on the individual PCs. For example, the PCs can bepolymerizable photochromic groups or photochromic groups that areadapted to be compatible with a host material (“compatibilizedphotochromic group”). Non-limiting examples of polymerizablephotochromic groups from which PC can be chosen and that are useful inconjunction with various non-limiting embodiments disclosed herein aredisclosed in U.S. Pat. No. 6,113,814, which is hereby specificallyincorporated by reference herein. Non-limiting examples of compatiblizedphotochromic groups from which PC can be chosen and that are useful inconjunction with various non-limiting embodiments disclosed herein aredisclosed in U.S. Pat. No. 6,555,028, which is hereby specificallyincorporated by reference herein.

Other suitable photochromic groups and complementary photochromic groupsare described in U.S. Pat. No. 6,080,338 at column 2, line 21 to column14, line 43; U.S. Pat. No. 6,136,968 at column 2, line 43 to column 20,line 67; U.S. Pat. No. 6,296,785 at column 2, line 47 to column 31, line5; U.S. Pat. No. 6,348,604 at column 3, line 26 to column 17, line 15;U.S. Pat. No. 6,353,102 at column 1, line 62 to column 11, line 64; andU.S. Pat. No. 6,630,597 at column 2, line 16 to column 16, line 23; thedisclosures of the aforementioned patents are incorporated herein byreference.

In addition to at least one lengthening agent (L), the photochromiccompounds can further comprise at least one group represented by R¹ thatis directly bonded to PC. Although not required, as previouslydiscussed, the at least one lengthening agent (L) can be indirectlybonded to PC through the at least one group represented by R¹. That is,L can be a substituent on at least one group R¹ that is bonded to PC.According to various non-limiting embodiments disclosed herein, R¹ canbe independently chosen for each occurrence from:

-   -   (i) hydrogen, C₁-C₁₂ alkyl, C₂-C₁₂ alkylidene, C₂-C₁₂        alkylidyne, vinyl, C₃-C₇ cycloalkyl, C₁-C₁₂ haloalkyl, allyl,        halogen, and benzyl that is unsubstituted or mono-substituted        with at least one of C₁-C₁₂ alkyl and C₁-C₁₂ alkoxy;    -   (ii) phenyl that is mono-substituted at the para position with        at least one substituent chosen from: C₁-C₇ alkoxy, linear or        branched chain C₁-C₂₀ alkylene, linear or branched chain C₁-C₄        polyoxyalkylene, cyclic C₃-C₂₀ alkylene, phenylene, naphthylene,        C₁-C₄ alkyl substituted phenylene, mono- or        poly-urethane(C₁-C₂₀)alkylene, mono- or        poly-ester(C₁-C₂₀)alkylene, mono- or        poly-carbonate(C₁-C₂₀)alkylene, polysilanylene, polysiloxanylene        and mixtures thereof, wherein the at least one substituent is        connected to an aryl group of a photochromic material;    -   (iii) —CH(CN)₂ and —CH(COOX₁)₂, wherein X₁ is chosen from at        least one of a lengthening agent L represented by Formula I        above, H, C₁-C₁₂ alkyl that is unsubstituted or mono-substituted        with phenyl, phenyl(C₁-C₁₂)alkyl that is mono-substituted with        C₁-C₁₂ alkyl or C₁-C₁₂alkoxy, and an aryl group that is        unsubstituted, mono- or di-substituted, wherein each aryl        substituent is independently chosen from C₁-C₁₂alkyl and C₁-C₁₂        alkoxy;    -   (iv) —CH(X₂)(X₃), wherein:        -   (A) X₂ is chosen from at least one of a lengthening agent L            represented by Formula I above, hydrogen, C₁-C₁₂alkyl and an            aryl group that is unsubstituted, mono- or di-substituted,            wherein each aryl substituent is independently chosen from            C₁-C₁₂ alkyl and C₁-C₁₂ alkoxy; and        -   (B) X₃ is chosen from at least one of —COOX₁, —COX₁, —COX₄,            and —CH₂OX₅, wherein:            -   (1) X₄ is chosen from at least one of morpholino,                piperidino, amino that is unsubstituted, mono- or                di-substituted with C₁-C₁₂ alkyl, and an unsubstituted,                mono or di-substituted group chosen from phenylamino and                diphenylamino, wherein each substituent is independently                chosen from C₁-C₁₂alkyl or C₁-C₁₂ alkoxy; and            -   (2) X₅ is chosen from a lengthening agent L represented                by Formula I above, hydrogen, —C(O)X₂, C₁-C₁₂ alkyl that                is unsubstituted or mono-substituted with (C₁-C₁₂)alkoxy                or phenyl, phenyl(C₁-C₁₂)alkyl that is mono-substituted                with (C₁-C₁₂)alkoxy, and an aryl group that is                unsubstituted, mono- or di-substituted, wherein each                aryl substituent is independently chosen from                C₁-C₁₂alkyl and C₁-C₁₂ alkoxy;    -   (v) an unsubstituted, mono-, di-, or tri-substituted aryl group,        such as phenyl, naphthyl, phenanthryl, or pyrenyl;        9-julolidinyl; or an unsubstituted, mono- or di-substituted        heteroaromatic group chosen from pyridyl, furanyl,        benzofuran-2-yl, benzofuran-3-yl, thienyl, benzothien-2-yl,        benzothien-3-yl, dibenzofuranyl, dibenzothienyl, carbazoyl,        benzopyridyl, indolinyl, and fluorenyl; wherein the substituents        are independently chosen for each occurrence from:        -   (A) a lengthening agent L represented by Formula I above;        -   (B) —C(O)X₆, wherein X₆ is chosen from at least one of: a            lengthening agent L represented by Formula I above, H,            C₁-C₁₂ alkoxy, phenoxy that is unsubstituted, mono- or            di-substituted with C₁-C₁₂ alkyl or C₁-C₁₂alkoxy, an aryl            group that is unsubstituted, mono- or di-substituted with            C₁-C₁₂ alkyl or C₁-C₁₂ alkoxy, an amino group that is            unsubstituted, mono- or di-substituted with C₁-C₁₂ alkyl,            and a phenylamino group that is unsubstituted, mono- or            di-substituted with C₁-C₁₂ alkyl or C₁-C₁₂ alkoxy;        -   (C) aryl, haloaryl, C₃-C₇ cycloalkylaryl, and an aryl group            that is mono- or di-substituted with C₁-C₁₂ alkyl or            C₁-C₁₂alkoxy;        -   (D) C₁-C₁₂ alkyl, C₃-C₇ cycloalkyl, C₃-C₇            cycloalkyloxy(C₁-C₁₂)alkyl, aryl(C₁-C₁₂)alkyl,            aryloxy(C₁-C₁₂)alkyl, mono- or            di-(C₁-C₁₂)alkylaryl(C₁-C₁₂)alkyl, mono- or            di-(C₁-C₁₂)alkoxyaryl(C₁-C₁₂)alkyl, haloalkyl, and            mono(C₁-C₁₂)alkoxy(C₁-C₁₂)alkyl;        -   (E) C₁-C₁₂ alkoxy, C₃-C₇ cycloalkoxy;            cycloalkyloxy(C₁-C₁₂)alkoxy; aryl(C₁-C₁₂)alkoxy,            aryloxy(C₁-C₁₂)alkoxy, mono- or            di-(C₁-C₁₂)alkylaryl(C₁-C₁₂)alkoxy, and mono- or            di-(C₁-C₁₂)alkoxyaryl(C₁-C₁₂)alkoxy;        -   (F) amido, amino, mono- or di-alkylamino, diarylamino,            piperazino, N—(C₁-C₁₂)alkylpiperazino, N-arylpiperazino,            aziridino, indolino, piperidino, morpholino, thiomorpholino,            tetrahydroquinolino, tetrahydroisoquinolino, pyrrolidyl,            hydroxy, acryloxy, methacryloxy, and halogen;        -   (G) —OX₇ and —N(X₇)₂, wherein X₇ is chosen from:            -   (1) a lengthening agent L represented by Formula I                above, hydrogen, C₁-C₁₂ alkyl, C₁-C₁₂acyl,                phenyl(C₁-C₁₂)alkyl, mono(C₁-C₁₂)alkyl substituted                phenyl(C₁-C₁₂)alkyl, mono(C₁-C₁₂ )alkoxy substituted                phenyl(C₁-C₁₂)alkyl; C₁-C₁₂ alkoxy(C₁-C₁₂)alkyl; C₃-C₇                cycloalkyl; mono(C₁-C₁₂)alkyl substituted C₃-C₇                cycloalkyl, C₁-C₁₂ haloalkyl, allyl, benzoyl,                mono-subsituted benzoyl, naphthoyl or mono-substituted                naphthoyl, wherein each of said benzoyl and naphthoyl                substituents are independently chosen from C₁-C₁₂ alkyl,                and C₁-C₁₂ alkoxy;            -   (2) —CH(X₈)X₉, wherein X₈ is chosen from a lengthening                agent L represented by Formula I above, H or                C₁-C₁₂alkyl; and X₉ is chosen from a lengthening agent L                represented by Formula I above, —CN, —CF₃, or —COOX₁₀,                wherein X₁₀ is chosen from a lengthening agent L                represented by Formula I above, H or C₁-C₁₂ alkyl;            -   (3) —C(O)X₆; and            -   (4) tri(C₁-C₁₂)alkylsilyl, tri(C₁-C₁₂)alkoxysilyl,                di(C₁-C₁₂)alkyl(C₁-C₁₂alkoxy)silyl, or                di(C₁-C₁₂)alkoxy(C₁-C₁₂ alkyl)silyl;        -   (H) —SX₁₁, wherein X₁₁ is chosen from a lengthening agent L            represented by Formula I above, C₁₋C₁₂alkyl, an aryl group            that is unsubstituted, or mono- or di-substituted with            C₁₋C₁₂alkyl, C₁₋C₁₂alkoxy or halogen;        -   (I) a nitrogen containing ring represented by Formula i:

-   -   -    wherein:            -   (1) n is an integer chosen from 0, 1, 2, and 3, provided                that if n is 0, U′ is U, and each U is independently                chosen for each occurrence from —CH₂—, —CH(X₁₂)—,                —C(X₁₂)₂₋, —CH(X₁₃)—, —C(X₁₃)₂—, and —C(X₁₂)(X₁₃)—,                wherein X₁₂ is chosen from a lengthening agent L                represented by Formula I above and C₁-C₁₂ alkyl, and X₁₃                is chosen from a lengthening agent L represented by                Formula I above, phenyl and naphthyl, and            -   (2) U′ is chosen from U, —O—, —S—, —S(O)—, —NH—,—N(X₁₂)—                or —N(X₁₃)—, and m is an integer chosen from 1, 2, and                3; and        -   (J) a group represented by one of Formula ii or iii:

-   -   -    wherein X₁₄, X₁₅, and X₁₆ are independently chosen for each            occurrence from a lengthening agent L represented by Formula            I above, C₁-C₁₂ alkyl, phenyl and naphthyl, or X₁₄ and X₁₅            together form a ring of 5 to 8 carbon atoms; p is an integer            chosen from 0, 1, or 2, and X₁₇ is independently chosen for            each occurrence from a lengthening agent L represented by            Formula I above, C₁-C₁₂ alkyl, C₁-C₁₂ alkoxy and halogen;

    -   (vi) an unsubstituted or mono-substituted group chosen from        pyrazolyl, imidazolyl, pyrazolinyl, imidazolinyl, pyrrolidinyl,        phenothiazinyl, phenoxazinyl, phenazinyl and acridinyl, wherein        each substituent is independently chosen from a lengthening        agent L represented by Formula I above, C₁-C₁₂ alkyl, C₁-C₁₂        alkoxy, phenyl, hydroxy, amino and halogen;

    -   (vii) a group represented by one of Formula iv or v:

-   -    wherein        -   (A) V′ is independently chosen in each formula from —O—,            —CH—, C₁-C₆ alkylene, and C₃-C₇ cycloalkylene,        -   (B) V is independently chosen in each formula from —O— or            —N(X₂₁)—, wherein X₂₁ is from a lengthening agent L            represented by Formula I above, hydrogen, C₁-C₁₂ alkyl, and            C₂-C₁₂ acyl, provided that if V is —N(X₂₁)—, V′ is —CH₂—,        -   (C) X₁₈ and X₁₉ are each independently chosen from a            lengthening agent L represented by Formula I above, hydrogen            and C₁-C₁₂ alkyl, and        -   (D) k is chosen from 0, 1, and 2, and each X₂₀ is            independently chosen for each occurrence from a lengthening            agent L represented by Formula I above, C₁-C₁₂ alkyl, C₁-C₁₂            alkoxy, hydroxy and halogen;    -   (viii) a group represented by Formula vi:

-   -    wherein        -   (A) X₂₂ is chosen from a lengthening agent L represented by            Formula I above, hydrogen and C₁-C₁₂ alkyl, and        -   (B) X₂₃ is chosen from a lengthening agent L represented by            Formula I above or an unsubstituted, mono-, or            di-substituted group chosen from naphthyl, phenyl, furanyl            and thienyl, wherein each substituent is independently            chosen for each occurrence from C₁-C₁₂alkyl, C₁-C₁₂alkoxy,            and halogen;    -   (ix) —C(O)X₂₄, wherein X₂₄ is chosen from a lengthening agent L        represented by Formula I above, hydroxy, C₁-C₁₂ alkyl, C₁-C₁₂        alkoxy, phenyl that is unsubstituted or mono-substituted with        C₁-C₁₂ alkyl or C₁-C₁₂alkoxy, amino that is unsubstituted, mono-        or di-substituted with at least one of C₁-C₁₂ alkyl, phenyl,        benzyl, and napthyl;    -   (x) —OX₇ and —N(X₇)₂, wherein X₇ is as set forth above;    -   (xi) —SX₁₁, wherein X₁₁ is as set forth above;    -   (xii) the nitrogen containing ring represented by Formula iv,        which is set forth above;    -   (xiii) the group represented by one of Formula v or vi, which        are set forth above; and    -   (xiv) immediately adjacent R¹ groups together a group        represented by one of Formula vii, viii, and ix:

-   -    wherein        -   (A) W and W′ are independently chosen for each occurrence            from —O—, —N(X₇)—, —C(X₁₄)—, —C(X₁₇)—, (wherein X₇, X₁₄, and            X₁₇ are as set forth above),        -   (B) X₁₄, X₁₅ and X₁₇ are as set forth above, and        -   (C) q is an integer chosen from 0, 1, 2, 3, and 4.

According to one non-limiting embodiment, the photochromic-dichroiccompound can be a photochromic pyran that is represented by Formula II:

wherein A is an aromatic ring or a fused aromatic ring chosen from:naphtho, benzo, phenanthro, fluorantheno, antheno, quinolino, thieno,furo, indolo, indolino, indeno, benzofuro, benzothieno, thiopheno,indeno-fused naphtho, heterocyclic-fused naphtho, and heterocyclic-fusedbenzo; and B and B′ each can be independently chosen from:

-   -   (i) hydrogen, C₁-C₁₂ alkyl, C₂-C₁₂ alkylidene, C₂-C₁₂alkylidyne,        vinyl, C₃-C₇ cycloalkyl, C₁-C₁₂ haloalkyl, allyl, halogen, and        benzyl that is unsubstituted or mono-substituted with at least        one of C₁-C₁₂ alkyl and C₁-C₁₂ alkoxy;    -   (ii) phenyl that is mono-substituted at the para position with        at least one substituent chosen from: C₁-C₇ alkoxy, linear or        branched chain C₁-C₂₀ alkylene, linear or branched chain C₁-C₄        polyoxyalkylene, cyclic C₃-C₂₀ alkylene, phenylene, naphthylene,        C₁-C₄ alkyl substituted phenylene, mono- or        poly-urethane(C₁-C₂₀)alkylene, mono- or        poly-ester(C₁-C₂₀)alkylene, mono- or        poly-carbonate(C₁-C₂₀)alkylene, polysilanylene, polysiloxanylene        and mixtures thereof, wherein the at least one substituent is        connected to an aryl group of a photochromic material;    -   (iii) —CH(CN)₂ and —CH(COOX₁)₂, wherein X₁ is as set forth        above;    -   (iv) —CH(X₂)(X₃), wherein X₂ and X₃ are as set forth above;    -   (v) an unsubstituted, mono-, di-, or tri-substituted aryl group,        such as phenyl, naphthyl, phenanthryl, or pyrenyl;        9-julolidinyl; or an unsubstituted, mono- or di-substituted        heteroaromatic group chosen from pyridyl, furanyl,        benzofuran-2-yl, benzofuran-3-yl, thienyl, benzothien-2-yl,        benzothien-3-yl, dibenzofuranyl, dibenzothienyl, carbazoyl,        benzopyridyl, indolinyl, and fluorenyl; wherein the substituents        are independently chosen for each occurrence from:        -   (A) a lengthening agent L represented by Formula I above;        -   (B) —C(O)X₆, wherein X₆ is as set forth above;        -   (C) aryl, haloaryl, C₃-C₇ cycloalkylaryl, and an aryl group            that is mono- or di-substituted with C₁-C₁₂ alkyl or            C₁-C₁₂alkoxy;        -   (D) C₁-C₁₂ alkyl, C₃-C₇ cycloalkyl, C₃-C₇            cycloalkyloxy(C₁-C₁₂)alkyl, aryl(C₁-C₁₂)alkyl,            aryloxy(C₁-C₁₂)alkyl, mono- or            di-(C₁-C₁₂)alkylaryl(C₁-C₁₂)alkyl, mono- or            di-(C₁-C₁₂)alkoxyaryl(C₁-C₁₂)alkyl, haloalkyl, and            mono(C₁-C₁₂)alkoxy(C₁-C₁₂)alkyl;        -   (E) C₁-C₁₂ alkoxy, C₃-C₇ cycloalkoxy;            cycloalkyloxy(C₁-C₁₂)alkoxy; aryl(C₁-C₁₂)alkoxy,            aryloxy(C₁-C₁₂)alkoxy, mono- or            di-(C₁-C₁₂)alkylaryl(C₁-C₁₂)alkoxy, and mono- or            di-(C₁-C₁₂)alkoxyaryl(C₁-C₁₂)alkoxy;        -   (F) amido, amino, mono- or di-alkylamino, diarylamino,            piperazino, N—(C₁-C₁₂)alkylpiperazino, N-arylpiperazino,            aziridino, indolino, piperidino, morpholino, thiomorpholino,            tetrahydroquinolino, tetrahydroisoquinolino, pyrrolidyl,            hydroxy, acryloxy, methacryloxy, and halogen;        -   (G) —OX₇ and —N(X₇)₂, wherein X₇ is as set forth above;        -   (H) —SX₁₁, wherein X₁₁ is as set forth above;        -   (I) the nitrogen containing ring represented by Formula i,            which is set forth above; and        -   (J) the group represented by one of Formula ii or iii, which            are set forth above;    -   (vi) an unsubstituted or mono-substituted group chosen from        pyrazolyl, imidazolyl, pyrazolinyl, imidazolinyl, pyrrodlinyl,        phenothiazinyl, phenoxazinyl, phenazinyl, and acridinyl, wherein        each substituent is independently chosen from a lengthening        agent L, C₁-C₁₂ alkyl, C₁-C₁₂ alkoxy, phenyl, hydroxy, amino or        halogen;    -   (vii) the group represented by one of Formula iv or v, which are        set forth above; and    -   (viii) the group represented by Formula vi, which is set forth        above.

Alternatively, B and B′ together can form: (a) an unsubstituted, mono-or di-substituted fluoren-9-ylidene, wherein each of saidfluoren-9-ylidene substituents are chosen from C₁-C₄ alkyl, C₁-C₄alkoxy, fluoro and chloro; (b) a saturated C₃-C₁₂ spiro-monocyclichydrocarbon ring, e.g., cyclopropylidene, cyclobutylidene,cyclopentylidene, cyclohexylidene, cycloheptylidene, cyclooctylidene,cyclononylidene, cyclodecylidene cycloundecylidene, cyclododecylidene;(c) a saturated C₇-C₁₂ spiro-bicyclic hydrocarbon rings, e.g.,bicyclo[2.2.1]heptylidene, i.e., norbornylidene, 1,7,7-trimethylbicyclo[2.2.1]heptylidene, i.e., bornylidene, bicyclo[3.2.1]octylidene,bicyclo[3.3.1]nonan-9-ylidene, bicyclo[4.3.2]undecane; or (d) asaturated C₇-C₁₂ spiro-tricyclic hydrocarbon rings, e.g.,tricyclo[2.2.1.0^(2,6)]heptylidene, tricyclo[3.3.1.1^(3,7)]decylidene,i.e., adamantylidene, and tricyclo[5.3.1.1^(2,6)]dodecylidene. Furtheraccording to various non-limiting embodiments discussed in more detailbelow, B and B′ together can form indolino or benzoindolino that isunsubstituted or substituted with at least one group represented by R².

Referring again to Formula II, according to various non-limitingembodiments, “i” can be an integer chosen from 0 to the total availablepositions on A, and each R² can be independently chosen for eachoccurrence from: (i) a lengthening agent L represented by Formula I(above) and (ii) a group represented by R¹ (above); provided that thephotochromic-dichroic compound represented by Formula II comprises atleast one lengthening agent (L) represented by Formula I above.

Thus, for example, in Formula II, “i” can be at least 1 and at least oneof the R² groups can be a lengthening agent L. Additionally oralternatively, the photochromic-dichroic compound can comprise at leastone R² group, at least one B group, or at least one B′ group that issubstituted with a lengthening agent L. Thus, for example and withoutlimitation, L can be directly bonded to the pyran group, for example,wherein i is at least 1 and R² is L, or it can be indirectly bonded tothe pyran group, for example, as a substituent on an R², B, or B′ groupsuch that L extends the pyran group in an activated state such that theabsorption ratio of the photochromic compound is enhanced as compared tothe unextended pyran group. For example, although not limiting herein,the B or B′ group can be a phenyl group that is mono-substituted with alengthening agent L.

For example, according to various non-limiting embodiments, thephotochromic-dichroic compound can be a naphtho[1,2-b]pyran representedby Formula III:

wherein: (a) at least one of: the R² substituent in the 6-position, theR² substituent in the 8-position, B and B′ comprises a lengthening agentL; (b) the R² substituent in the 6-position together with the R²substituent in the 5-position forms a group represented by one ofFormula x to Formula xiv:

wherein K is chosen from —O—, —S—, —N(X₇)—; and an unsubstituted C or aC substituted with alkyl, hydroxy, alkoxy, oxo, or aryl; K′ is —C—,—O—,or —N(X₇)—; K″ is chosen from —O— or —N(X₇)—; X₂₅ is a group representedby R² (which is set forth above in detail); X₂₆ can be chosen fromhydrogen, alkyl, aryl, or together form benzo or naphtho; and each X₂₇is chosen from alkyl and aryl or together are oxo; provided that atleast one of: the R² substituent in the 8-position, X₂₅, K, K′, K″, B orB′ comprises a lengthening agent L; or (c) the R² substituent in the6-position together with the R² substituent in the 7-position from anaromatic group chosen from benzeno and naphtho, provided that at leastone of: the R² substituent in the 8-position, B and B′ comprises alengthening agent L.

Further, according to other non-limiting embodiments, thephotochromic-dichroic compound can be an indeno-fusednaphtho[1,2-b]pyran represented by Formula IV:

wherein K is as set forth above, and at least one of: the R² substituentin the 11-position, the R² substituent in the 7-position, K, B and B′comprises a lengthening agent L. Further, according to one specificnon-limiting embodiment, at least of: the R² substituent in the11-position and the R² substituent in the 7-position is a lengtheningagent L.

According to other non-limiting embodiments, the photochromic-dichroiccompound can be a naphtho[2,1-b]pyran represented by Formula V:

wherein at least one of: the R² substituent in the 6-position, the R²substituent in the 7-position, B, and B′ comprises a lengthening agentL. More specifically, according to one non-limiting embodiment, at leastone of: the R² substituent in the 6-position and the R² substituent inthe 7-position is a lengthening agent L.

Further, according to still other non-limiting embodiments, thephotochromic-dichroic compound can be a benzopyran comprising astructure represented by Formula VI:

wherein: (a) at least one of: the R² substituent in the 5-position, theR² substituent in the 7-position, B or B′ comprises a lengthening agentL; or (b) at least one of: the R substituent in the 5-position and theR² substituent in the 7-position, together with an immediately adjacentR² substituent, (i.e., the R² substituent in the 7-position togetherwith an R² substituent in the 6- or 8-positions, or the R² substituentin the 5-position together with an R substituent in the 6-position)forms a group represented by Formula x to xiv (set forth above),provided that only one of the R² substituent in the 5-position and theR² substituent in the 7-position join together with the R² substituentin the 6-position, and provided that at least one of: the R² substituentin the 5-position, the R² substituent in the 7-position, X₂₅, K, K′, K″,B or B′ comprises a lengthening agent L.

A general reaction sequence for forming photochromic-dichroic compoundsthat can be used in various non-limiting embodiments disclosed hereinand that are generally represented by Formula II above is depicted belowin Reaction Sequence A.

In Reaction Sequence A, Part 1, 4-fluorobenzophenone, which isrepresented by Formula α₁, can be reacted under nitrogen in theanhydrous solvent dimethyl sulfoxide (DMSO) with a lengthening agent Lrepresented by Formula α₂, to form an L substituted ketone representedby Formula α₃. It will be appreciated by those skilled in the art that4-fluorobenzophenone can either be purchased or prepared byFriedel-Crafts methods known in the art. For example, see thepublication Friedel-Crafts and Related Reactions, George A. Olah,Interscience Publishers, 1964, Vol. 3, Chapter XXXI (Aromatic KetoneSynthesis), and “Regioselective Friedel-Crafts Acylation of1,2,3,4-Tetrahydroquinoline and Related Nitrogen Heterocycles: Effect onNH Protective Groups and Ring Size” by Ishihara, Yugi et al, J. Chem.Soc., Perkin Trans. 1, pages 3401 to 3406, 1992.

As depicted in Part 2 of Reaction Sequence A, the L substituted ketonerepresented by Formula α₃ can be reacted with sodium acetylide in asuitable solvent, such as but not limited to anhydrous tetrahydrofuran(THF), to form the corresponding propargyl alcohol (represented byFormula α₄).

In Part 3 of Reaction Sequence A, the propargyl alcohol represented byFormula α₄ can be coupled with a hydroxy substituted A group(represented by Formula α₅) to form the photochromic pyran representedby Formula α₆ according to one non-limiting embodiment disclosed herein.Optionally, the A group can be substituted with one or more R² groups,each of which may comprise a lengthening agent L that is the same ordifferent from the remaining L substituents. Non-limiting examples of Aand R² groups that are suitable for use in conjunction with variousnon-limiting embodiments disclosed herein are set forth above in detail.Non-limiting examples of general reaction sequences for forminghydroxylated A groups that are substituted with at least one lengtheningagent L, are shown below in Reaction Sequences B, C, and D.

Although Reaction Sequence A depicts a general reaction sequence forforming a photochromic compound represented by Formula II and having Band B′ groups selected from L substituted phenyl and phenyl, it will beappreciated by those skilled in the art that photochromic compoundsgenerally represented by Formula II and having B and B′ groups otherthan those shown in Formula α₆ above, and which optionally can besubstituted with one or more L groups or one or more R² groupscomprising L, can be prepared from commercially available ketones, or byreaction of an acyl halide with a substituted or unsubstituted materialsuch as naphthalene or a heteroaromatic compound. Non-limiting examplesof B and B′ substituent groups that are suitable for use in conjunctionwith various non-limiting embodiments disclosed herein are set forthabove in detail.

Reaction Sequences B, C and D depict three different general reactionsequences for forming hydroxylated A groups that are substituted with atleast one lengthening agent L, that can be used in the formation ofphotochromic pyrans according to various non-limiting embodimentsdisclosed herein. For example, although not limiting herein, asdiscussed above in Reaction Sequence A, the resulting L substitutedhydroxylated A group can be coupled with propargyl alcohol to form aphotochromic pyran according to various non-limiting embodimentsdisclosed herein. Further, as discussed above, optionally, the A groupcan also be substituted with one or more additional R² groups, each ofwhich may comprise a lengthening agent L that is the same or differentfrom the remaining Ls.

In Reaction Sequence B, the hydroxlylated A group represented by Formulaβ₁ is reacted with the L substituted piperidine represented by Formulaβ₂ in the presence of an alkyl lithium, such as but not limited tomethyllithium (MeLi), in anhydrous tetrahydrofuran to produce the Lsubstituted R² group attached to the hydroxylated A group represented byFormula β₃. Further, as indicated above, the A group may also besubstituted with one or more additional R² groups, each of which mayalso comprise a lengthening agent L that is the same or different fromthe remaining Ls. Further, K can be chosen from —O—, —S—, —N(X₇)— orcarbon that is substituted or unsubstituted. For example, K can be acarbon that is di-substituted with methyl or can be substituted with anethyl group and a hydroxyl group.

In Reaction Sequence C, the R² substituted hydroxylated A grouprepresented by Formula χ₁ is reacted with the L substituted phenolrepresented by Formula χ₂ in an esterification reaction in the presenceof dicyclohexylcarbodiimide in methylene chloride to produce the Lsubstituted R² group attached to the hydroxylated A group represented byFormula χ₃. Further, as indicated in Reaction Sequence C, the grouprepresented by Formula χ₃ optionally can be substituted with one or moreadditional R² groups, each of which may also comprise a lengtheningagent L that is the same or different from the remaining Ls.

In Reaction Sequence D (below), the hydroxy substituted naphtholrepresented by Formula δ₁ is reacted with chlorine to form the compoundrepresented by Formula δ₂. The compound represented by Formula δ₂ isreacted with the L substituted piperidine represented by Formula δ₃ toform the material represented by Formula δ₄. The material represented byFormula δ₄ is reduced in a hydrogen atmosphere over a palladium oncarbon catalyst to form the L substituted R² group attached to thehydroxylated A group represented by Formula δ₅.

Reaction Sequences E and F demonstrate two different methods of forminga naphthopyran substituted with a lengthening agent L to form aphotochromic naphthopyran according to various non-limiting embodimentsdisclosed herein.

In Reaction Sequence E, the hydroxy substituted A group represented byFormula ε₁, which is optionally substituted with at least one R² group,is reacted with the hydroxy substituted piperidine represented byFormula ε₂ in the presence of an alkyl lithium, such as but not limitedto methyllithium (MeLi), in anhydrous tetrahydrofuran to produce the4-hydroxy piperidinyl attached to the hydroxylated A group representedby Formula ε₃. The compound represented by Formula ε₃ is then coupledwith the propargyl alcohol represented by Formula ε₄ to form the4-hydroxy piperidinyl attached to the indeno-fused naphthopyranrepresented by Formula ε₅. The naphthopyran represented by Formula ε₅can be further reacted, as indicated by path (1) Reaction Sequence E, inan acetylation reaction using a tertiary amine, such as but not limitedto triethylamine, in a solvent, such as but not limited to methylenechloride, with the L substituted compound represented by Formula ε₆ toproduce the L substituted piperidinyl attached to the indeno-fusednaphthopyran according to one non-limiting embodiment disclosed hereinand represented by Formula ε₇. Alternatively, as indicated by path (2),the naphthopyran represented by Formula ε₅ can be reacted with the Lsubstituted compound represented by Formula ε₈ to produce the Lsubstituted piperidinyl attached to the indeno-fused naphthopyranaccording to one non-limiting embodiment disclosed herein andrepresented by Formula ε₉. Further, as indicated in Reaction Sequence E,the L substituted piperidinyl attached to the indeno-fused naphthopyransrepresented by Formula ε₇ and Formula ε₉ can optionally be substitutedwith one or more additional R² groups, each of which may compriselengthening agent L that is the same or different from the remaining Ls.

In Reaction Sequence F (below), the hydroxylated A group represented byFormula φ₁ is coupled with the propargyl alcohol represented by Formulaφ₂ to produce the naphthopyran represented by Formula φ₃. Thenaphthopyran by Formula φ₃ is then reacted with the L substitutedphenylamine of Formula φ₄ to produce the L substituted phenylamineattached to the naphthopyran represented by Formula φ₅ according tovarious non-limiting embodiments disclosed herein. Non-limiting examplesof suitable B and B′ substituent groups are set forth above in detail.

Although not limiting herein, in the hydroxy substituted A grouprepresented by Formulae β₁ and ε₁ (which are set forth in ReactionSequences B and E, respectively), K can be a carbon that isdi-substituted with methyl to form2,3-dimethoxy-7,7-dimethyl-7H-benzo[c]fluoren-5-ol. Those skilled in theart will recognize numerous methods of making such a hydroxy substitutedA group. For example, and without limitation, one method of forming2,3-dimethoxy-7,7-dimethyl-7H-benzo[c]fluoren-5-ol is set forth in step2 of Example 9 of U.S. Pat. No. 6,296,785, which is hereby specificallyincorporated by reference. More specifically, as set forth in step 2 ofExample 9 of U.S. Pat. No. 6,296,785, one non-limiting method of forming2,3-dimethoxy-7,7-dimethyl-7H-benzo[c]fluoren-5-ol is as follows:

In a first step, 1,2-dimethoxybenzene (92.5 grams) and a solution ofbenzoyl chloride (84.3 grams) in 500 milliliters (mL) of methylenechloride is added to a reaction flask fitted with a solid additionfunnel under a nitrogen atmosphere. Solid anhydrous aluminum chloride(89.7 grams) is added to the reaction mixture with occasionally coolingof the reaction mixture in an ice/water bath. The reaction mixture isstirred at room temperature for 3 hours. The resulting mixture is pouredinto 300 mL of a 1:1 mixture of ice and 1N hydrochloric acid and stirredvigorously for 15 minutes. The mixture is extracted twice with 100 mLmethylene chloride. The organic layers are combined and washed with 50mL of 10 weight percent sodium hydroxide followed by 50 mL of water. Themethylene chloride solvent is removed by rotary evaporation to give ayellow solid. Recrystallization from 95 percent ethanol yields 147 gramsof beige needles having a melting point of 103-105° C. The product isbelieved to have a structure consistent with 3,4,-dimethoxybenzophenone.

In a second step, potassium t-butoxide (62 grams) and 90 grams of theproduct from preceding Step 1, is added to a reaction flask containing300 mL of toluene under a nitrogen atmosphere. The mixture is heated toreflux and dimethyl succinate (144.8 grams) is added dropwise over 1hour. The mixture is refluxed for 5 hours and cooled to roomtemperature. 300 mL of water is added to the reaction mixture andvigorously stirred for 20 minutes. The aqueous and organic phasesseparate and the organic phase is extracted with 100 mL portions ofwater three times. The combined aqueous layers are washed with 50 mLportions of chloroform three times. The aqueous layer is acidified to pH2 with 6N hydrochloric acid and a precipitate forms and is removed byfiltration. The aqueous layer is extracted with three 100 mL portions ofchloroform. The organic extracts are combined and concentrated by rotaryevaporation. The resulting oil is believed to have a structureconsistent with a mixture of (E and Z)4-(3,4-dimethoxyphenyl)-4-phenyl-3-methoxycarbonyl-3-butenoic acids.

In a third step, the product from preceding Step 2 (8.6 grams), 5 mL ofacetic anhydride, and 50 mL of toluene are added to a reaction flaskunder a nitrogen atmosphere. The reaction mixture is heated to 110° C.for 6 hours and cooled to room temperature, and the solvents (tolueneand acetic anhydride) are removed by rotary evaporation. The residue isdissolved in 300 mL of methylene chloride and 200 mL of water. Solidsodium carbonate is added to the biphasic mixture until bubbling ceased.The layers separate and the aqueous layer is extracted with two 50 mLportions of methylene chloride. The organic layers are combined and thesolvent (methylene chloride) is removed by rotary evaporation to yield athick red oil. The oil is dissolved in warm methanol and chilled at 0°C. for 2 hours. The resulting crystals are collected by vacuumfiltration, washed with cold methanol to produce 5 grams of a producthaving a melting point of 176-177° C. The recovered solid product isbelieved to have structures consistent with a mixture of1-(3,4-dimethoxyphenyl)-2-methoxycarbonyl-4-acetoxynaphthalene and1-phenyl-2-methoxycarbonyl-4-acetoxy-6,7-dimethoxynaphthalene.

In a fourth step, five (5) grams of the product mixture from precedingStep 3, 5 mL of 12M hydrochloric acid, and 30 mL of methanol arecombined in a reaction flask and heated to reflux for 1 hour. Thereaction mixture is cooled and the resulting precipitate is collected byvacuum filtration and washed with cold methanol. The product is purifiedby filtering through a plug of silica gel using a 2:1 mixture of hexaneand ethyl acetate as the eluant. Concentration of the filtrate by rotaryevaporation yields 3 grams of a beige solid that is believed to have astructure consistent with1-phenyl-2-methoxycarbonyl-6,7-dimethoxynaphth-4-ol.

In a fifth step, a reaction flask is charged with 2.8 grams of theproduct of preceding Step 4 under a nitrogen atmosphere. Anhydroustetrahydrofuran (40 mL) is added to the flask. The reaction mixture iscooled in a dry ice/acetone bath and 41 mL of a methyl magnesiumchloride solution (1M in tetrahydrofuran) is added dropwise over 15minutes. The resulting yellow reaction mixture is stirred at 0° C. for 2hours and slowly warmed to room temperature. The reaction mixture ispoured into 50 mL of an ice/water mixture. Ether (20 mL) is added, andthe layers separate. The aqueous layer is extracted with two 20 mLportions of ether, and the organic portions are combined and washed with30 mL of water. The organic layer is dried over anhydrous magnesiumsulfate and concentrated by rotary evaporation. The resulting oil istransferred into a reaction vessel (fitted with a Dean-Stark trap)containing 50 mL of toluene to which two drops of dodecylbenzenesulfonic acid are added. The reaction mixture is heated to reflux for 2hours and cooled. The toluene is removed via rotary evaporation to yield2 grams of the desired compound.

According to another non-limiting embodiment, the photochromic-dichroiccompound can be a photochromic spiro-pyran or spiro-oxazine that isrepresented by Formula VII:

wherein:

-   -   (a) A is chosen from naphtho, benzo, phenanthro, fluorantheno,        antheno, quinolino, thieno, furo, indolo, indolino, indeno,        benzofuro, benzothieno, thiopheno, indeno-fused naphtho,        heterocyclic-fused naphtho, and heterocyclic-fused benzo;    -   (b) Y is C or N;    -   (c) SP is a spiro-group chosen from indolino and benzindolino;        and    -   (d) i is an integer chosen from 0 to the total number of        available positions on A, r is an integer chosen from 0 to the        total number available positions on SP, provided that the sum of        i+r is at least one, and each R³ is independently chosen for        each occurrence from:        -   (i) a lengthening agent L represented by Formula I above;            and        -   (ii) a group represented by R¹ above;            provided that the photochromic-dichroic compound represented            by Formula VII comprises at least one lengthening agent (L)            represented by Formula I above.

As discussed above with respect to the photochromic compounds generallyrepresented by Formula II disclosed herein, the photochromic compoundsgenerally represented by Formula VII can be extended at any availableposition by substitution with L or an R³ group substituted with L,and/or in any desired direction by numerous combinations ofsubstitutions of available positions with L or R³ groups substitutedwith L. Thus, for example, although not limiting herein, thephotochromic compounds generally represented by Formula VII can beextended by substituting the SP group with L or an R³ group substitutedwith L, and/or by substituting the A group with L or an R³ groupsubstituted with L so as to provided a desired average absorption ratioof the photochromic compound. For example, although not limiting herein,according to certain non-limiting embodiments the photochromic-dichroiccompound can be represented by Formula VIII:

wherein each R″ is independently chosen for each occurrence fromhydrogen, a substituted or unsubstituted alkyl, cycloalkyl, arylalkyl,or together form cycloalkyl that is substituted or unsubstituted; R′″ ischosen from an alkyl, aryl, or arylalkyl group that is unsubstituted orsubstituted with at least one of: (i) —CH(CN)₂ or —CH(COOX₁)₂; (ii)—CH(X₂)(X₃); and (iii) —C(O)X₂₄ (wherein X₁, X₂, X₃, and X₂₄ are as setforth above); and (iv) halogen, hydroxy, ester, or amine; and wherein atleast one of i and r is at least 1, and at least one R³ comprises L.Further, according to one non-limiting embodiment, at least one R³ is L.As discussed above with respect to Formula VII, Y in Formula VIII can bechosen from C or N. For example, according to various non-limitingembodiments, Y can be C, and the photochromic compound can be aspiro(indolino)pyran. According to other non-limiting embodiments, Y canbe N, and the photochromic compound can be a spiro(indolino)oxazine.

According to another non-limiting embodiment, the photochromic-dichroiccompound can be represented by Formula IX:

wherein at least one of: the R³ in the 6-position or the R³ in the7-position comprises a lengthening agent L. Further, according to onespecific non-limiting embodiment, at least one of the R³ group in the6-position or the R³ group 7-position of Formula IX is a lengtheningagent L.

According to still another non-limiting embodiment, thephotochromic-dichroic compound can be represented by Formula X:

wherein at least the R³ in the 7-postion comprises a lengthening agentL. Further, according to one specific non-limiting embodiment, the R³group in the 7-position is a lengthening agent L.

According to yet another non-limiting embodiment, thephotochromic-dichroic compound can be represented by Formula XI:

wherein at least the R³ group in the 6-position comprises a lengtheningagent L. Further, according to various non-limiting embodiments, the R³group in the 6-position is a lengthening agent L.

A general reaction sequence for synthesizing photochromic-dichroiccompounds that can be used in various non-limiting embodiments disclosedherein and that are generally represented by Formula VII is depictedbelow in Reaction Sequence G.

Reaction Sequence G, Part 1 depicts a general nitrosation process inwhich the hydroxylated A group represented by of Formula γ₁ is reactedwith sodium nitrite in the presence of an acid, such as but not limitedto acetic acid, to produce the nitroso-substituted A group representedby Formula γ₂. Suitable non-limiting examples of A groups includenaphtho, benzo, phenanthro, fluorantheno, antheno, quinolino,indeno-fused naphtho, heterocyclic-fused naphtho, and heterocyclic-fusedbenzo. Optionally, the A group can be substituted with one or more R³groups, each of which may comprise a lengthening agent L that is thesame or different from the remaining Ls.

In Part 2 of Reaction Sequence G, the nitroso-substituted A grouprepresented by Formula γ₂ is coupled with a Fischer's base representedby Formula γ₃. The coupling is conducted in a solvent, such as but notlimited to absolute ethanol, and heated under reflux conditions toproduce the photochromic oxazine represented by Formula γ₄ according tovarious non-limiting embodiments disclosed herein.

The general nitrosation process shown in Part 1 of Reaction Sequence Gis more specifically set forth in the following two sequences (ReactionSequences H and I), which generally depict two nitroso phenol synthesisprocesses for producing nitroso-substituted A groups, which canoptionally be substituted with at least one R³, that can be used incoupling reactions to produce the oxazine products of the presentinvention. As illustrated in Path (2) of Sequences H and I, prior toreacting with NaNO₂, the intermediate compound can be further reactedwith one or more other reactants to form a suitable lengthening agent Lon the A group.

More specifically, in Reaction Sequence H, the carboxylic acid of thehydroxylated A group represented by Formula η₁ is converted into esterof hydroxylated A group represented by Formula η₂. Ester of thehydroxylated A group represented by Formula η₂ can then be reacted withsodium nitrite in the presence of an acid, such as but not limited toacetic acid, to produce the nitroso-substituted A group of Formula η₃.Alternatively, as shown in Path (2), ester of hydroxylated A grouprepresented by Formula η₂ can be reacted with 4-piperidinoaniline(represented by Formula η₄) under basic conditions to produce the Lsubstituted compound represented by Formula η₅. The L substitutedcompound represented by Formula η₅ is then subjected to the nitrosationreaction to produce the L and nitroso substituted A group representedFormula η₆. Further, the L and nitroso substituted A group optionallycan be substituted with one or more R³ groups, each of which cancomprise a lengthening agent L which is the same or different from theremaining Ls.

As discussed above with respect to Reaction Sequence H, in ReactionSequence I (below) the carboxylic acid of the hydroxylated A grouprepresented by Formula τ₁ is converted into the ester of thehydroxylated the A group represented by Formula τ₂. The ester ofhydroxylated A group represented by Formula τ₂ can then be reacted withsodium nitrite in the presence of an acid, such as but not limited toacetic acid, to produce the nitroso-substituted A group of Formula τ₃.Alternatively, as shown in Path (2), ester of hydroxylated the A grouprepresented by Formula τ₂ can be reacted with 4-phenyl aniline(represented by Formula τ₄) under basic conditions to produce the Lsubstituted 4-phenyl aniline represented by Formula τ₅. The Lsubstituted 4-phenyl aniline represented by Formula τ₅ is then subjectedto the nitrosation reaction to produce the L and nitroso substituted Agroup represented Formula τ₆. As discussed above, the (L substituted(nitroso substituted A groups)), optionally can be substituted with oneor more R³ groups, each of which can comprise a lengthening agent Lwhich is the same or different from the remaining Ls.

More specific reaction sequences for synthesizing the photochromiccompounds according to various non-limiting embodiments disclosed hereinare depicted below in Reaction Sequences J and K.

In Reaction Sequence J (below), a nitrosophenol represented by Formulaφ₁ is reacted in methanol with a lengthening agent L, which ispiperazino phenol (represented by Formula φ₂), to form the L substitutednitrosonaphthol represented by Formula φ₃. As depicted in ReactionSequence J, the L substituted nitrosonaphthol can be further substitutedwith one or more R groups, each of which may comprise a lengtheningagent L that is the same or different from the remaining L substituents.The L substituted nitrosonaphthol represented by Formula φ₃ is thencoupled by heating with the Fischer's base represented by Formula φ₄ toproduce the L substituted naphthoxazine represented by Formula φ₅.

With continued reference to Reaction Sequence J, the L substitutednaphthoxazine represented by Formula φ₅ can be further extended byreacting the L substituted naphthoxazine with another L substitutedcompound represented by Formula φ₆ to produce a naphthoxazinerepresented by Formula φ₇ according to various non-limiting embodimentsdisclosed herein. Further, as previously discussed and as depicted inReaction Sequence J, naphthoxazine represented by Formula φ₇ optionallycan be substituted with one or more R³ groups, each of which maycomprise a lengthening agent L that is the same or different from theremaining Ls.

As illustrated above in Reaction Sequence J, generally after couplingthe nitrosophenol with the Fischer's base, the resultant naphthoxazinecan be further reacted with one or more other reactants to extend thenaphthoxazine with lengthening agent L. However, those skilled in theart will appreciate that, additionally or alternatively, prior tocoupling the nitrosophenol with the Fischer's base, the nitrosophenolcan be reacted to substitute the nitrosophenol with one or morelengthening agents L (for example as shown above in Reaction Sequences Hand I). Further, such L substituted nitrosophenols can be coupled with aFischer's base to form an L-substituted naphthoxazine as generallydepicted in Reaction Sequence K, below.

More specifically, in Reaction Sequence K, an L substitutedpiperidinylnaphthol represented by Formula κ₁ is reacted withtrialkoxymethane and heated to form the L and formyl substitutednaphthol represented by Formula κ₂. The compound represented by Formulaκ₂ is then reacted with the Fischer's base (represented by Formula κ₃)to produce the L substituted spironaphthopyran represented by Formula κ₄according to various non-limiting embodiments disclosed herein.

As previously discussed, generally after coupling the nitrosophenol withthe Fischer's base (for example as shown in Reaction Sequence J), theresultant naphthoxazine can be further reacted with one or more otherreactants to extend the naphthoxazine with lengthening agent L. Severalnon-limiting examples of such extension are provided in the generalizedReaction Sequence M below.

More specifically, in Reaction Sequence M (below), three paths foradding a lengthening agent L to a naphthoxazine to produce thephotochromic oxazines according to various non-limiting embodimentsdisclosed herein. In the first path (1), the naphthoxazine representedby Formula μ₁ is reacted with hydroxyphenylpiperazine to produce thematerial represented by Formula μ₂. The material represented by Formulaμ₂ is benzoylated with hexylbenzoylchloride to produce the materialrepresented by Formula μ₃. In the second path (2), the materialrepresented by Formula μ₁ undergoes hydrolysis and is converted into thematerial of Formula μ₄. In an esterification reaction with a phenol-likematerial in the presence of dicyclohexylcarbodiimide in methylenechloride the material represented by Formula μ₄ is converted into thematerial represented by Formula μ₅ having the tetrahydropyran protectinggroup. The material represented by Formula μ₅ is deprotected by a dilutesolution of hydrochloric acid in an alcoholic solvent, such as but notlimited to ethanol, to form the material represented by Formula μ₆. Thematerial represented by Formula μ₆ is reacted with a cholesterolchloroformate to form the material represented by Formula μ₇ In thethird path (3), the material represented by Formula μ₆ is benzoylatedwith 4-phenylbenzoylchloride to form the material represented by Formulaμ₈.

According to another non-limiting embodiment the photochromic-dichroiccompound can be represented by Formula XII:

wherein

-   -   (a) A is chosen from naphtho, benzo, phenanthro, fluorantheno,        antheno, quinolino, thieno, furo, indolo, indolino, indeno,        benzofuro, benzothieno, thiopheno, indeno-fused naphtho,        heterocyclic-fused naphtho, and heterocyclic-fused benzo;    -   (b) J is a spiro-alicyclic ring;    -   (c) each D is independently chosen from O, N(Z), C(X₄), C(CN)₂,        wherein Z is independently chosen for each occurrence from        hydrogen, C₁-C₆ alkyl, cycloalkyl and aryl;    -   (d) G is group chosen from alkyl, cycloalkyl, and aryl, which        can be unsubstituted or substituted with at least one        substituent R⁴;    -   (e) E is —O— or is —N(R⁵)—, wherein R⁵ is chosen from:        -   (i) hydrogen, C₁-C₁₂ alkyl, C₂-C₁₂ alkene, C₂-C₁₂alkyne,            vinyl, C₃-C₇ cycloalkyl, C₁-C₁₂ haloalkyl, allyl, halogen,            and benzyl that is unsubstituted or mono-substituted with at            least one of C₁-C₁₂ alkyl and C₁-C₁₂ alkoxy;        -   (ii) phenyl that is mono-substituted at the para position            with at least one substituent chosen from: C₁-C₇ alkoxy,            linear or branched chain C₁-C₂₀ alkylene, linear or branched            chain C₁-C₄ polyoxyalkylene, cyclic C₃-C₂₀ alkylene,            phenylene, naphthylene, C₁-C₄ alkyl substituted phenylene,            mono- or poly-urethane(C₁-C₂₀)alkylene, mono- or            poly-ester(C₁-C₂₀)alkylene, mono- or            poly-carbonate(C₁-C₂₀)alkylene, polysilanylene,            polysiloxanylene and mixtures thereof, wherein the at least            one substituent is connected to an aryl group of a            photochromic material;        -   (iii) —CH(CN)₂ and —CH(COOX₁)₂, wherein X₁ is as set forth            above;        -   (iv) —CH(X₂)(X₃), wherein X₂ and X₃ are as set forth above;        -   (v) an unsubstituted, mono-, di-, or tri-substituted aryl            group, such as phenyl, naphthyl, phenanthryl, or pyrenyl;            9-julolidinyl; or an unsubstituted, mono- or di-substituted            heteroaromatic group chosen from pyridyl, furanyl,            benzofuran-2-yl, benzofuran-3-yl, thienyl, benzothien-2-yl,            benzothien-3-yl, dibenzofuranyl, dibenzothienyl, carbazoyl,            benzopyridyl, indolinyl, and fluorenyl; wherein the            substituents are independently chosen for each occurrence            from:            -   (A) a lengthening agent L represented by Formula I                above;            -   (B) —C(O)X₆, wherein X₆ is as set forth above;            -   (C) aryl, haloaryl, C₃-C₇ cycloalkylaryl, and an aryl                group that is mono- or di-substituted with C₁-C₁₂ alkyl                or C₁-C₁₂ alkoxy;            -   (D) C₁-C₁₂ alkyl, C₃-C₇ cycloalkyl, C₃-C₇                cycloalkyoxy(C₁-C₁₂)alkyl, aryl(C₁-C₁₂)alkyl,                aryloxy(C₁-C₁₂)alkyl, mono- or                di-(C₁-C₁₂)alkylaryl(C₁-C₁₂)alkyl, mono- or                di-(C₁-C₁₂)alkoxyaryl(C₁-C₁₂)alkyl, haloalkyl, and                mono(C₁-C₁₂)alkoxy(C₁-C₁₂)alkyl;            -   (E) C₁-C₁₂ alkoxy, C₃-C₇ cycloalkoxy,                cycloalkyloxy(C₁-C₁₂)alkoxy, aryl(C₁-C₁₂)alkoxy,                aryloxy(C₁-C₁₂)alkoxy, mono- or                di-(C₁-C₁₂)alkylaryl(C₁-C₁₂)alkoxy, and mono- or                di-(C₁-C₁₂)alkoxyaryl(C₁-C₁₂)alkoxy;            -   (F) amido, amino, mono- or di-alkylamino, diarylamino,                piperazino, N—(C₁-C₁₂)alkylpiperazino, N-arylpiperazino,                aziridino, indolino, piperidino, morpholino,                thiomorpholino, tetrahydroquinolino,                tetrahydroisoquinolino, pyrrolidyl, hydroxy, acryloxy,                methacryloxy, and halogen;            -   (G) —OX₇ and —N(X₇)₂, wherein X₇ is as set forth above;            -   (H) —SX₁₁, wherein X₁₁ is as set forth above;            -   (I) a nitrogen containing ring represented by Formula i,                which is set forth above; and            -   (J) a group represented by one of Formula ii or iii,                which are set forth above;        -   (vi) an unsubstituted or mono-substituted group chosen from            pyrazolyl, imidazolyl, pyrazolinyl, imidazolinyl,            pyrrodlinyl, phenothiazinyl, phenoxazinyl, phenazinyl, or            acridinyl, wherein each substituent is independently chosen            from a lengthening agent L, C₁-C₁₂ alkyl, C₁-C₁₂ alkoxy,            phenyl, hydroxy, amino or halogen;        -   (vii) a group represented by one of Formula iv or v, which            are set forth above;        -   (viii) a group represented by Formula vi, which is set forth            above; and        -   (ix) a lengthening agent L represented by Formula I (above);            and    -   (f) i is an integer chosen from 0 to the total available        positions on A, and each R⁴ is independently chosen for each        occurrence from:        -   (i) a lengthening agent L represented by Formula I; and        -   (ii) a group represented by R¹;            provided the photochromic-dichroic compound represented by            Formula XII comprises at least one lengthening agent (L)            represented by Formula I above.

As discussed with respect to the photochromic-dichroic compounds setforth above, the photochromic-dichroic compounds generally representedby Formula XII can be extended at any available position by substitutionwith L or an R⁴ group substituted with L, and/or in any desireddirection by numerous combinations of substitutions of availablepositions with L or R⁴ groups substituted with L. Thus, for example,although not limiting herein, the fulgides disclosed herein can beextended by selecting at least one of D, G, and at least one R⁴ to be Lor a group substituted with L, so as to enhance the average absorptionratio of the fulgide in at least the activated state. Further, althoughnot limiting herein, as shown discussed in more detail below, when E isN—R⁵, R⁵ can be L or can be a group substituted with L. For example,according to one non-limiting embodiment, the photochromic-dichroiccompound can be represented by Formula XIII:

wherein at least one of: R⁵, G or R⁴ is a lengthening agent L.

A general reaction sequence for synthesizing the photochromic-dichroiccompounds that can be used in various non-limiting embodiments disclosedherein and that are represented by Formula XII above is depicted belowin Reaction Sequence N. In Reaction Sequence N (below), an alicyclicketone represented by Formula ν₁ is reacted with dimethyl succinaterepresented by Formula ν₂ in a Stobbe Condensation to produce thehalf-ester product represented by Formula ν₃. The half-ester productrepresented by Formula ν₃ is esterified to form the diester productrepresented by Formula ν₄. The diester of Formula ν₄ is reacted with acarbonyl-substituted A group represented by Formula ν₅ in the StobbeCondensation to produce the half-ester material represented by Formulaν₆. As indicated Formula ν₅, the carbonyl-substituted A group can alsobe substituted with one or more R⁴ groups, each of which can comprise alengthening agent L which is the same or different from the remaining Lsubstituents. The half-ester material represented by Formula ν₇ ishydrolyzed to produce the diacid material represented by Formula ν₇ Thediacid of Formula ν₇ is reacted with acetyl chloride in an ether and/ortetrahydrofuran solvent to form the anhydride represented by Formula ν₈.

As shown in Path (1) of Reaction Sequence N (below), the anhydride ofFormula ν₈ can be reacted with an amino substituted lengthening agent Land subsequently reacted with acetyl chloride under reflux conditions toproduce the photochromic fulgimide compound represented by Formula ν₉according to one non-limiting embodiment disclosed herein.Alternatively, as shown in Path (2), the anhydride of Formula ν₈ can bereacted with ammonia followed by acetyl chloride to produce thephotochromic fulgide compound according to various non-limitingembodiments disclosed herein and represented by Formula ν₁₀. Further,the photochromic fulgide compound of Formula ν₁₀ can be further reactedwith an appropriate reactant to form the photochromic fulgide compoundof Formula ν₁₁ according to various non-limiting embodiments disclosedherein, wherein the nitrogen is substituted with an R⁵ group. Further,according to various non-limiting embodiments, the R⁵ group can be alengthening agent L, or can comprise a substituent group that issubstituted with a lengthening agent L.

Reaction Sequences P, Q and T illustrate three general reaction schemesfor substituting a lengthening agent L at various locations on afulgide.

In Reaction Sequence P, the hydroxylated compound represented by Formulaπ₁ undergoes the Friedel-Crafts reaction to form thecarbonyl-substituted group represented by Formula π₂. The materialrepresented by Formula π₂ is reacted as described above for the materialrepresented by Formula ν₅ in Reaction Sequence N to form thehydroxyphenyl substituted thiophenofused fulgide represented by Formulaπ₃ in Reaction Sequence P. The fulgide represented by Formula π₃ isbenzoylated with 4-phenylbenzoyl chloride to form the thermallyreversible, photochromic compound according to one non-limitingembodiment disclosed herein and represented by Formula π₄. Withadditional reference to Formula XII above, as shown in Formula π₄, the Agroup is thiopheno that is substituted with a lengthening agent L. Aspreviously discussed, according to various non-limiting embodiments (andas shown below in Reaction Sequence Q), the R⁵ group in Formula π₄ canbe a lengthening agent L, or can comprise another substituent group thatis substituted with a lengthening agent L. Further, group G can also bea lengthening agent L or can be another substituent group that issubstituted with a lengthening agent L (for example, as shown below inReaction Sequence T).

In Reaction Sequence Q, the fulgide represented by Formula θ₁ can bemade in accordance with Reaction Sequence N, with appropriatemodifications that will be recognized by those skilled in the art. InFormula θ₁, the R⁵ group attached to the nitrogen atom is a methyl esterof para-amino benzoic acid. The methyl ester of para-amino benzoic acidis then reacted with 4-aminodiazobenzene, to form the thermallyreversible, photochromic compound represented by Formula θ₂ according toone non-limiting embodiment disclosed herein. As previously discussed,R⁵ group can be a lengthening agent L or can be another substituentgroup that is substituted with L. Further, as previously discussed (andas depicted in Reaction Sequence P above) the A group of the thermallyreversible, photochromic compound represented by Formula θ₂, optionallycan be substituted with one or more R⁴ groups, each of which maycomprise a lengthening agent L that is the same or different from theremaining L substituents. Further, as shown below in Reaction Sequence T(below), the G group in Formula θ₂ can also be a lengthening agent L orcan be another substituent group that is substituted with a lengtheningagent L.

In Reaction Sequence T, the fulgide represented by Formula τ₁ can bemade in accordance with Reaction Sequence N, with appropriatemodifications that will be recognized by those skilled in the art. Thefulgide represented by formula τ₁ can then be reacted with para-aminobenzoylchloride to form the thermally reversible, photochromic compoundaccording to one non-limiting embodiment disclosed herein andrepresented by Formula τ₂. As previously discussed (and as depicted inReaction Sequence Q above), the R⁵ group of the thermally reversible,photochromic compound represented by Formula τ₂ can be a lengtheningagent L or can be another substituent group that is substituted with L.Further, as previously discussed (and as depicted in Reaction Sequence Pabove) the A group of the thermally reversible, photochromic compoundrepresented by Formula τ₂, optionally can be substituted with one ormore R⁴ groups, each of which may comprise a lengthening agent L that isthe same or different from the remaining Ls.

As previously discussed, one non-limiting embodiment disclosed hereinprovides an optical element comprising a substrate and at least one atleast partially aligned photochromic-dichroic compound connected to atleast a portion of the substrate and having an average absorption ratiogreater than 2.3 in an activated state as determined according to theCELL METHOD. Additionally, according to this non-limiting embodiment,the optical element can further comprise at least one orientationfacility having a at least a first general direction connected to atleast a portion of the substrate, and at least a portion of the at leastone at least partially aligned photochromic-dichroic compound can be atleast partially aligned by interaction with the orientation facility.

As used herein the term “orientation facility” means a mechanism thatcan facilitate the positioning of one or more other structures that areexposed, directly and/or indirectly, to at least a portion thereof. Asused herein the term “order” means bring into a suitable arrangement orposition, such as aligning with another structure or material, or bysome other force or effect. Thus, as used herein the term “order”encompasses both contact methods of ordering a material, such as byaligning with another structure or material, and non-contact methods ofordering a material, such as by exposure to an external force or effect.The term order also encompasses combinations of contact and non-contactmethods.

For example, in one non-limiting embodiment, the at least a portion ofthe at least one at least partially aligned photochromic-dichroiccompound that is at least partially aligned by interaction with the atleast one orientation facility can be at least partially aligned suchthat the long-axis of the photochromic-dichroic compound in theactivated state is essentially parallel to at least the first generaldirection of the at least one orientation facility. According to anothernon-limiting embodiment, the at least a portion of the at least one atleast partially aligned photochromic-dichroic compound that is at leastpartially aligned by interaction with at least a portion of the at leastone orientation facility is bound to or reacted with the portion of theat least one orientation facility. As used herein with reference toorder or alignment of a material or structure, the term “generaldirection” refers to the predominant arrangement or orientation of thematerial, compound or structure. Further, it will be appreciated bythose skilled in the art that a material, compound or structure can havea general direction even though there is some variation within thearrangement of the material, compound or structure, provided that thematerial, compound or structure has at least one predominatearrangement.

As discussed above, the orientation facilities according to variousnon-limiting embodiments disclosed herein can have at least a firstgeneral direction. For example, the orientation facility can comprise afirst ordered region having a first general direction and at least onesecond ordered region adjacent the first ordered region having a secondgeneral direction that is different from the first general direction.Further, the orientation facility can have a plurality of regions, eachof which has a general direction that is the same or different from theremaining regions so as to form a desired pattern or design.Additionally, the at least one orientation facility can comprise one ormore different types of orientation facilities. Non-limiting examples oforientation facilities that can be used in conjunction with this andother non-limiting embodiments disclosed herein include at least partialcoatings comprising an at least partially ordered alignment medium, atleast partially ordered polymer sheets, at least partially treatedsurfaces, Langmuir-Blodgett films, and combinations thereof.

For example, although not limiting herein, according to one non-limitingembodiment, the orientation facility can comprise an at least partialcoating comprising an at least partially ordered alignment medium.Non-limiting examples of suitable alignment media that can be used inconjunction with various non-limiting embodiments disclosed hereininclude photo-orientation materials, rubbed-orientation materials, andliquid crystal materials. Non-limiting methods of ordering at least aportion of the alignment medium are described herein below in detail.

As discussed above, according to various non-limiting embodiments, thealignment medium can be a liquid crystal material. Liquid crystalmaterials, because of their structure, are generally capable of beingordered or aligned so as to take on a general direction. Morespecifically, because liquid crystal molecules have rod- or disc-likestructures, a rigid long axis, and strong dipoles, liquid crystalmolecules can be ordered or aligned by interaction with an externalforce or another structure such that the long axis of the moleculestakes on an orientation that is generally parallel to a common axis. Forexample, although not limiting herein, it is possible to align themolecules of a liquid crystal material with a magnetic field, anelectric field, linearly polarized infrared radiation, linearlypolarized ultraviolet radiation, linearly polarized visible radiation,or shear forces. It is also possible to align liquid crystal moleculeswith an oriented surface. That is, liquid crystal molecules can beapplied to a surface that has been oriented, for example by rubbing,grooving, or photo-alignment methods, and subsequently aligned such thatthe long axis of each of the liquid crystal molecules takes on anorientation that is generally parallel to the general direction oforientation of the surface. Non-limiting examples of liquid crystalmaterials suitable for use as alignment media according to variousnon-limiting embodiments disclosed herein include liquid crystalpolymers, liquid crystal pre-polymers, liquid crystal monomers, andliquid crystal mesogens. As used herein the term “pre-polymer” meanspartially polymerized materials.

Liquid crystal monomers that are suitable for use in conjunction withvarious non-limiting embodiments disclosed herein include mono- as wellas multi-functional liquid crystal monomers. Further, according tovarious non-limiting embodiments disclosed herein, the liquid crystalmonomer can be a cross-linkable liquid crystal monomer, and can furtherbe a photocross-linkable liquid crystal monomer. As used herein the term“photocross-linkable” means a material, such as a monomer, a pre-polymeror a polymer, that can be cross-linked on exposure to actinic radiation.For example, photocross-linkable liquid crystal monomers include thoseliquid crystal monomers that are cross-linkable on exposure toultraviolet radiation and/or visible radiation, either with or withoutthe use of polymerization initiators.

Non-limiting examples of cross-linkable liquid crystal monomers suitablefor use in accordance with various non-limiting embodiments disclosedherein include liquid crystal monomers having functional groups chosenfrom acrylates, methacrylates, allyl, allyl ethers, alkynes, amino,anhydrides, epoxides, hydroxides, isocyanates, blocked isocyanates,siloxanes, thiocyanates, thiols, urea, vinyl, vinyl ethers and blendsthereof. Non-limiting examples of photocross-linkable liquid crystalmonomers suitable for use in the at least partial coatings of thealignment facilities according to various non-limiting embodimentsdisclosed herein include liquid crystal monomers having functionalgroups chosen from acrylates, methacrylates, alkynes, epoxides, thiols,and blends thereof.

Liquid crystal polymers and pre-polymers that are suitable for use inconjunction with various non-limiting embodiments disclosed hereininclude main-chain liquid crystal polymers and pre-polymers andside-chain liquid crystal polymers and pre-polymers. In main-chainliquid crystal polymers and pre-polymers, rod- or disc-like liquidcrystal mesogens are primarily located within the polymer backbone. Inside-chain polymers and pre-polymers, the rod- or disc-like liquidcrystal mesogens primarily are located within the side chains of thepolymer. Additionally, according to various non-limiting embodimentsdisclosed herein, the liquid crystal polymer or pre-polymer can becross-linkable, and further can be photocross-linkable.

Non-limiting examples of liquid crystal polymers and pre-polymers thatare suitable for use in accordance with various non-limiting embodimentsdisclosed herein include, but are not limited to, main-chain andside-chain polymers and pre-polymers having functional groups chosenfrom acrylates, methacrylates, allyl, allyl ethers, alkynes, amino,anhydrides, epoxides, hydroxides, isocyanates, blocked isocyanates,siloxanes, thiocyanates, thiols, urea, vinyl, vinyl ethers, and blendsthereof. Non-limiting examples of photocross-linkable liquid crystalpolymers and pre-polymers that are suitable for use in the at leastpartial coatings of the alignment facilities according to variousnon-limiting embodiments disclosed herein include those polymers andpre-polymers having functional groups chosen from acrylates,methacrylates, alkynes, epoxides, thiols, and blends thereof.

Liquid crystals mesogens that are suitable for use in conjunction withvarious non-limiting embodiments disclosed herein include thermotropicliquid crystal mesogens and lyotropic liquid crystal mesogens. Further,non-limiting examples of liquid crystal mesogens that are suitable foruse in conjunction with various non-limiting embodiments disclosedherein include columatic (or rod-like) liquid crystal mesogens anddiscotic (or disc-like) liquid crystal mesogens.

Non-limiting examples of photo-orientation materials that are suitablefor use as an alignment medium in conjunction with various non-limitingembodiments disclosed include photo-orientable polymer networks.Specific non-limiting examples of suitable photo-orientable polymernetworks include azobenzene derivatives, cinnamic acid derivatives,coumarine derivatives, ferulic acid derivatives, and polyimides. Forexample, according to one non-limiting embodiment, the orientationfacility can comprise at least one at least partial coating comprisingan at least partially ordered photo-orientable polymer network chosenfrom azobenzene derivatives, cinnamic acid derivatives, coumarinederivatives, ferulic acid derivatives, and polyimides. Specificnon-limiting examples of cinnamic acid derivatives that can be used asan alignment medium in conjunction with various non-limiting embodimentsdisclosed herein include polyvinyl cinnamate and polyvinyl esters ofparamethoxycinnamic acid.

As used herein the term “rubbed-orientation material” means a materialthat can be at least partially ordered by rubbing at least a portion ofa surface of the material with another suitably textured material. Forexample, although not limiting herein, in one non-limiting embodiment,the rubbed-orientation material can be rubbed with a suitably texturedcloth or a velvet brush. Non-limiting examples of rubbed-orientationmaterials that are suitable for use as an alignment medium inconjunction with various non-limiting embodiments disclosed hereininclude (poly)imides, (poly)siloxanes, (poly)acrylates, and(poly)coumarines. Thus, for example, although not limiting herein, theat least partial coating comprising the alignment medium can be an atleast partial coating comprising a polyimide that has been rubbed withvelvet or a cloth so as to at least partially order at least a portionof the surface of the polyimide.

As discussed above, the at least one orientation facility according tocertain non-limiting embodiments disclosed herein can comprise an atleast partially ordered polymer sheet. For example, although notlimiting herein, a sheet of polyvinyl alcohol can be at least partiallyordered by stretching the sheet, and there after the sheet can be bondedto the at least a portion a surface of the optical substrate to form theorientation facility. Alternatively, the ordered polymer sheet can bemade by a method that at least partially orders the polymer chainsduring fabrication, for example and without limitation, by extrusion.Further, the at least partially ordered polymer sheet can be formed bycasting or otherwise forming a sheet of a liquid crystal material andthereafter at least partially ordering the sheet for example, butexposing the sheet to at least one of a magnetic field, an electricfield, or a shear force. Still further, the at least partially orderedpolymer sheet can be made using photo-orientation methods. For exampleand without limitation, a sheet of a photo-orientation material can beformed, for example by casting, and thereafter at least partiallyordered by exposure to linearly polarized ultraviolet radiation. Stillother non-limiting methods of forming at least partially ordered polymersheets are described herein below.

Still further, the orientation facilities according to variousnon-limiting embodiments disclosed herein can comprise an at leastpartially treated surface. As used herein, the term “treated surface”refers to at least a portion of a surface that has been physicallyaltered to create at least one ordered region on least a portion of thesurface. Non-limiting examples of at least partially treated surfacesinclude at least partially rubbed surfaces, at least partially etchedsurfaces, and at least partially embossed surfaces. Further, the atleast partially treated surfaces can be patterned, for example using aphotolithographic or an interferographic process. Non-limiting examplesof at least partially treated surfaces that are useful in forming theorientation facilities according to various non-limiting embodimentsdisclosed herein include, chemically etched surfaces, plasma etchedsurfaces, nanoetched surfaces (such as surfaces etched using a scanningtunneling microscope or an atomic force microscope), laser etchedsurfaces, and electron-beam etched surfaces.

In one specific non-limiting embodiment, wherein the orientationfacility comprises an at least partially treated surface, imparting theorientation facility can comprise depositing a metal salt (such as ametal oxide or metal fluoride) onto at least a portion of a surface, andthereafter etching the deposit to form the orientation facility.Non-limiting examples of suitable techniques for depositing a metal saltinclude plasma vapor deposition, chemical vapor deposition, andsputtering. Non-limiting examples of etching processes are set forthabove.

As used herein the term “Langmuir-Blodgett films” means one or more atleast partially ordered molecular films on a surface. For example,although not limiting herein, a Langmuir-Blodgett film can be formed bydipping a substrate into a liquid one or more times so that it is atleast partially covered by a molecular film and then removing thesubstrate from the liquid such that, due to the relative surfacetensions of the liquid and the substrate, the molecules of the molecularfilm are at least partially ordered in a general direction. As usedherein, the term molecular film refers to monomolecular films (i.e.,monolayers) as well as films comprising more than one monolayer.

In addition to the orientation facilities described above, the opticalelements according to various non-limiting embodiments disclosed hereincan further comprise at least one at least partial coating comprising anat least partially ordered alignment transfer material interposedbetween the at least one orientation facility and thephotochromic-dichroic compound (or at least partial coating comprisingthe same). Still further, the optical elements can comprise a pluralityof at least partial coatings comprising an alignment transfer interposedbetween the at least one orientation facility and thephotochromic-dichroic compound. For example, although not limitingherein, the optical element can comprise at least one orientationfacility comprising an at least partial coating comprising an at leastpartially ordered alignment medium connected to at least a portion ofthe optical substrate, and at least one at least partial coatingcomprising an at least partially ordered alignment transfer materialconnected to at least a portion of the orientation facility. Further,according to this non-limiting embodiment, the at least onephotochromic-dichroic compound can be at least partially aligned byinteraction with the at least partially ordered alignment transfermaterial. More specifically, although not limiting herein, in onenon-limiting embodiment, at least a portion of the alignment transfermaterial can be aligned by interaction with at least a portion of the atleast partially ordered alignment medium, and at least a portion of theat least one photochromic-dichroic compound can be aligned byinteraction with the at least a partially aligned portion of thealignment transfer material. That is, the alignment transfer materialcan facilitate the propagation or transfer of a suitable arrangement orposition from the orientation facility to the at least onephotochromic-dichroic compound.

Non-limiting examples of alignment transfer materials that are suitablefor use in conjunction with various non-limiting embodiments disclosedherein include, without limitation, those liquid crystal materialsdescribed above in connection with the alignment media disclosed herein.As previously discussed, it is possible to align the molecules of aliquid crystal material with an oriented surface. That is, a liquidcrystal material can be applied to a surface that has been oriented andsubsequently aligned such that the long axis of the liquid crystalmolecules takes on an orientation that is generally parallel to thegeneral direction of orientation of the surface. Thus, according tovarious non-limiting embodiments disclosed herein wherein the alignmenttransfer material comprises a liquid crystal material, the liquidcrystal material can be at least partially ordered by aligning the atleast a portion of the liquid crystal material with at least a portionof the orientation facility such that the long axis of the molecules ofat least a portion of the liquid crystal material are generally parallelto at least a first general direction of the orientation facility. Inthis manner, the general direction of the orientation facility can betransferred to the liquid crystal material, which in turn can transferthe general direction to another structure or material. Further, if theat least one orientation facility comprises a plurality of regionshaving general directions that together form a design or pattern (aspreviously described), that design or pattern can be transferred to theliquid crystal material by aligning the liquid crystal material with thevarious regions of the orientation facility as discussed above.Additionally, although not required, according to various non-limitingembodiments disclosed herein, at least a portion of the liquid crystalmaterial can be exposed to at least one of: a magnetic field, anelectric field, linearly polarized infrared radiation, linearlypolarized ultraviolet radiation, and linearly polarized visibleradiation while being at least partially aligned with at least a portionof the orientation facility.

Still further, in addition to the at least one at least partiallyaligned photochromic-dichroic compound connected to the at least aportion of the substrate, the optical element according to variousnon-limiting embodiments disclosed herein can comprise at least one atleast partially ordered anisotropic material connected to the at least aportion of the at least one surface of the substrate. That is, accordingto certain non-limiting embodiments the optical element comprises asubstrate, at least one at least partially aligned photochromic-dichroiccompound connected to at least a portion of the substrate, the at leastone photochromic-dichroic compound having an average absorption ratiogreater than 2.3 in an activated state as determined according to theCELL METHOD, and at least one at least partially ordered anisotropicmaterial connected to the at least a portion of the at least one surfaceof the substrate.

As used herein the term “anisotropic” means having at least one propertythat differs in value when measured in at least one different direction.Thus, “anisotropic materials” are materials that have at least oneproperty that differs in value when measured in at least one differentdirection. Non-limiting examples of anisotropic materials that aresuitable for use in conjunction with various non-limiting embodimentsdisclosed herein include, without limitation, those liquid crystalmaterials described above.

According to various non-limiting embodiments, at least a portion of theat least one at least partially aligned photochromic-dichroic compoundcan be at least partially aligned by interaction with the at least oneat least partially ordered anisotropic material. For example, althoughnot limiting herein, at least a portion of the at least onephotochromic-dichroic compound can be aligned such that the long-axis ofthe photochromic-dichroic compound in the dichroic state is essentiallyparallel to the general direction of the anisotropic material. Further,although not required, the at least one photochromic-dichroic compoundcan be bound to or reacted with at least a portion of the at least oneat least partially ordered anisotropic material.

Further, according to various non-limiting embodiments disclosed herein,the at least one at least partially aligned photochromic-dichroiccompound and the at least one at least partially ordered anisotropicmaterial can be present as an least partial coating on at least aportion of the substrate. For example, according to one non-limitingembodiment, the at least one at least partially ordered anisotropicmaterial can be a liquid crystal material, and the at least one at leastpartially aligned photochromic-dichroic compound and the at least one atleast partially ordered anisotropic material can be present as an leastpartial liquid crystal coating on at least a portion of the substrate.According to another non-limiting embodiment, the at least partialcoating can be a phase-separated polymer coating comprising a matrixphase and a guest phase distributed in the matrix phase. Although notlimiting herein, according to this non-limiting embodiment, the matrixphase can comprise an at least partially ordered liquid crystal polymer.Further, according to this non-limiting embodiment, guest phase cancomprise the at least partially ordered anisotropic material and atleast a portion of the at least one at least partially alignedphotochromic-dichroic compound. Still further, as discussed above, theat least one at least partially aligned photochromic-dichroic compoundcan be at least partially aligned by interaction with the at leastpartially ordered anisotropic material.

In another non-limiting embodiment, the at least partial coating cancomprise an interpenetrating polymer network. According to thisnon-limiting embodiment, the at least one at least partially orderedanisotropic material and a polymeric material can form aninterpenetrating polymer network, wherein at least a portion of thepolymeric material interpenetrates with at least a portion of the atleast partially ordered anisotropic material. As used herein the term“interpenetrating polymer network” means an entangled combination ofpolymers, at least one of which is cross-linked, that are not bonded toeach other. Thus, as used herein, the term interpenetrating polymernetwork includes semi-interpenetrating polymer networks. For example,see L. H. Sperling, Introduction to Physical Polymer Science, John Wiley& Sons, New York (1986) at page 46. Further, according to thisnon-limiting embodiment, at least a portion of the at least one at leastpartially aligned photochromic-dichroic compound can be at leastpartially aligned with the at least partially ordered anisotropicmaterial. Still further, according to this non-limiting embodiment, thepolymeric material can be isotropic or anisotropic, provided that, onthe whole, the at least partial coating is anisotropic. Methods offorming such at least partial coatings are described in more detailherein below.

Still other non-limiting embodiments disclosed herein provide an opticalelement comprising a substrate, at least one at least partially orderedorientation facility connected to at least a portion of the substrate,and an at least partial coating connected to at least a portion of theat least partially ordered orientation facility, the at least partialcoating comprising at least one anisotropic material that is at leastpartially aligned with at least a portion of the at least partiallyordered orientation facility and at least one photochromic-dichroiccompound that is at least partially aligned with at least a portion ofthe at least partially aligned anisotropic material.

As previously discussed, the orientation facilities according to variousnon-limiting embodiments disclosed herein can comprise a first orderedregion having a first general direction and at least one second orderedregion adjacent the first region having a second general direction thatis different from the first general direction. Further, the orientationfacility can comprise multiple ordered regions having multiple generaldirections that together create a specific design or pattern.Non-limiting examples of orientation facilities that are suitable foruse in conjunction with this non-limiting embodiment are described abovein detail. Additionally, according to various non-limiting embodimentdisclosed herein, an at least partial coating comprising an alignmenttransfer material can be positioned between the at least one orientationfacility and the at least partial coating comprising the anisotropicmaterial and the at least one photochromic-dichroic compound. Further,the general direction or pattern of the at least one orientationfacility can be transferred to the alignment transfer material byalignment, which, in turn, can transfer the general direction of theorientation facility to the at least partial coating comprising theanisotropic material and the at least one photochromic-dichroic compoundby alignment. That is, the anisotropic material of the at least partialcoating can be at least partially aligned with the at least partiallyaligned alignment transfer material. Further, the at least onephotochromic-dichroic compound can be at least partially aligned byinteraction with the at least partially aligned anisotropic material.

Further, according to various non-limiting embodiments disclosed herein,the at least one anisotropic material can be adapted to allow the atleast one photochromic-dichroic compound to switch from a first state tothe second state at a desired rate. Generally speaking conventionalphotochromic compounds can undergo a transformation from one isomericform to another in response to actinic radiation, with each isomericform having a characteristic absorption spectrum. Thephotochromic-dichroic compounds according to various non-limitingembodiments disclosed herein undergo a similar isomeric transformation.The rate or speed at which this isomeric transformation (and the reversetransformation) occurs depends, in part, upon the properties of thelocal environment surrounding the photochromic-dichroic compound (thatis, the “host”). Although not limiting herein, it is believed by theinventors the rate of transformation of the photochromic-dichroiccompound will depend, in part, upon the flexibility of the chainsegments of the host, that is, the mobility or viscosity of the chainsegments of the host. In particular, while not limiting herein, it isbelieved that the rate of transformation of the photochromic-dichroiccompound will generally be faster in hosts having flexible chainsegments than in host having stiff or rigid chain segments. Therefore,according to certain non-limiting embodiments disclosed herein, whereinthe anisotropic material is a host, the anisotropic material can beadapted to allow the photochromic-dichroic compound to transform betweenvarious isomeric states at desired rates. For example, although notlimiting herein, the anisotropic material can be adapted by adjustingone or more of the molecular weight and the cross-link density of theanisotropic material.

According to another non-limiting embodiment, the at least partialcoating comprising at least one anisotropic material and at least onephotochromic-dichroic compound can be a phase-separated polymer coatingcomprising matrix phase, for example and without limitation, a liquidcrystal polymer, and guest phase distributed within the matrix phase.Further, according to this non-limiting embodiment, the guest phase cancomprise the anisotropic material. Still further, according to thisnon-limiting embodiment, the majority of the at least onephotochromic-dichroic compound can be contained within the guest phaseof the phase-separated polymer coating. As previously discussed, becausethe transformation rate of the at least one photochromic-dichroiccompound depends, in part, on the host in which it is contained,according to this non-limiting embodiment, the rate of transformation ofthe at least one photochromic-dichroic compound will depend, largely, onthe properties of the guest phase.

For example, one non-limiting embodiment provides an optical elementcomprising a substrate, at least one orientation facility connected toat least a portion of a surface of the substrate, and an at leastpartial coating connected to at least a portion of the at least oneorientation facility and comprising a phase-separated polymer. Accordingto this non-limiting embodiment, the phase-separated polymer cancomprise a matrix phase, at least a portion of which is at leastpartially aligned with at least portion of the at least one orientationfacility, and a guest phase comprising an anisotropic material dispersedwithin the matrix phase. Further according to this non-limitingembodiment, at least a portion of the anisotropic material of the guestphase can be at least partially aligned with at least portion of the atleast one orientation facility and at least one photochromic-dichroiccompound can be at least partially aligned with at least a portion ofthe anisotropic material. Still further, according to variousnon-limiting embodiments disclosed herein, the matrix phase of thephase-separated polymer can comprise a liquid crystal polymer, and theanisotropic material of the guest phase can be chosen from liquidcrystal polymers and liquid crystal mesogens. Non-limiting examples ofsuch materials are set forth in detail above. Additionally, while notlimiting herein, according to this non-limiting embodiment, the at leastpartial coating comprising the phase-separated polymer can besubstantially haze-free. Haze is defined as the percentage oftransmitted light that deviates from the incident beam by more than 2.5degrees on average according to ASTM D 1003 Standard Test Method of Hazeand Luminous Transmittance of Transparent Plastics. An example of aninstrument on which haze measurements according to ASTM D 1003 can bemade is Haze-Gard Plus™ made by BYK-Gardener.

Further, although not limiting herein, according to other non-limitingembodiments the at least one photochromic-dichroic compound can beencapsulated or coated with an at least partially ordered host materialand then the encapsulated or coated photochromic-dichroic compound canbe dispersed within another material. For example, although not limitingherein, the at least one photochromic-dichroic compound can beencapsulated or overcoated with an at least partially orderedanisotropic material having relatively flexible chain segments, such asan at least partially ordered liquid crystal material, and thereafterdispersed or distributed in another material having relatively rigidchain segments. For example, the encapsulated photochromic-dichroiccompound can be dispersed or distributed in a liquid crystal polymerhaving relatively rigid chain segments and thereafter the mixture can beapplied to a substrate to form a coating.

According to still another non-limiting embodiment, the at least partialcoating comprising at least one anisotropic material and at least onephotochromic-dichroic compound can be interpenetrating polymer networkcoating. For example, the at least partial coating can comprise apolymeric material that interpenetrates with at least a portion of theat least one anisotropic material, and at least a portion of the atleast one photochromic-dichroic compound can be at least partiallyaligned with the at least partially aligned anisotropic material.Methods of forming such interpenetrating network coatings are describedbelow in more detail.

Still other non-limiting embodiments disclosed herein provide an opticalelement comprising a substrate, a first at least partial coatingcomprising an at least partially ordered alignment medium connected toat least a portion of at least one surface of the substrate, a second atleast partial coating comprising an alignment transfer materialconnected to and at least partially aligned with at least a portion ofthe at least partially ordered alignment medium, and a third at leastpartial coating connected to at least a portion of the at leastpartially ordered alignment transfer material, the third at leastpartial coating comprising at least one anisotropic material that is atleast partially aligned with at least a portion of the at leastpartially aligned alignment transfer material and at least onephotochromic-dichroic compound that is at least partially aligned withat least a portion of the at least partially aligned anisotropicmaterial.

Although not limiting herein, according to various non-limitingembodiments, the first at least partial coating comprising the at leastpartially ordered alignment medium can have a thickness that varieswidely depending upon the final application and/or the processingequipment employed. For example, in one non-limiting embodiment, thethickness of the at least partial coating comprising the at leastpartially ordered alignment medium can range from at least 0.5nanometers to 10,000 nanometers. In another non-limiting embodiment, theat least partial coating comprising the at least partially orderedalignment medium can have a thickness ranging from at least 0.5nanometers to 1000 nanometers. In still another non-limiting embodiment,the at least partial coating comprising the at least partially orderedalignment medium can have a thickness ranging from at least 2 nanometersto 500 nanometers. In yet another non-limiting embodiment, the at leastpartial coating comprising the at least partially ordered alignmentmedium can have a thickness ranging from 100 nanometers to 500nanometers. Additionally, according to various non-limiting embodiments,the optical element can comprise a plurality of at least partialcoatings comprising an at least partially ordered alignment medium.Further each of the plurality of at least partial coatings can have thesame or a different thickness as the other at least partial coatings ofthe plurality.

Further, according to various non-limiting embodiments disclosed herein,the second at least partial coating comprising the alignment transfermaterial can have a thickness that varies widely depending upon thefinal application and/or the processing equipment employed. For example,in one non-limiting embodiment, the thickness of the at least partialcoating comprising the at least partially ordered alignment transfermaterial can range from 0.5 microns to 1000 microns. In anothernon-limiting embodiment, the at least partial coating comprising the atleast partially ordered alignment transfer material can have a thicknessranging from 1 to 25 microns. In still another non-limiting embodiment,the at least partial coating comprising the at least partially orderedalignment transfer material can have a thickness ranging from 5 to 20microns. Additionally, according to various non-limiting embodiments,the optical element can comprise a plurality of at least partialcoatings comprising an alignment transfer material. Further each of theplurality of at least partial coatings can have the same or a differentthickness as the other at least partial coatings of the plurality.

Still further, according to various non-limiting embodiments disclosedherein, the third at least partial coating comprising the anisotropicmaterial and the at least one photochromic-dichroic compound can have athickness that varies widely depending upon the final application and/orthe processing equipment employed. In one non-limiting embodiment, theat least partial coating comprising the at least partially alignedanisotropic material and the at least one photochromic-dichroic compoundcan have a thickness of at least 0.5 microns to 1000 microns. Accordingto other non-limiting embodiments, the third at least partial coatingcan have a thickness ranging from 1 micron to 25 microns. According tostill other non-limiting embodiments, the third at least partial coatingcan have a thickness ranging from 5 microns to 20 microns. Additionally,according to various non-limiting embodiments, the optical element cancomprise a plurality of at least partial coatings comprising an at leastpartially aligned anisotropic material and at least one dichroicmaterial. Further each of the plurality of at least partial coatings canhave the same or a different thickness as the other at least partialcoatings of the plurality. Non-limiting examples of suitablephotochromic-dichroic compounds are described above in detail.

Further, according to various non-limiting embodiments, in addition tothe third at least partial coating, either or both of the first andsecond at least partial coatings can comprise photochromic-dichroiccompounds that are the same or different from the photochromic-dichroiccompounds of the third at least partial coating. Still further,according to various non-limiting embodiments, any of the at leastpartial coatings described above can further comprise at least oneadditive, at least one conventional dichroic compound and/or at leastone conventional photochromic compound. Non-limiting examples ofsuitable additives, conventional dichroic compounds, and conventionalphotochromic compounds are set forth above. Further, as previouslydiscussed, in addition to the first, second, and third at least partialcoatings described above, the optical elements according to variousnon-limiting embodiments disclosed herein can further comprise primercoatings, anti-reflective coatings, photochromic coatings, linearlypolarizing coatings, circularly polarizing coatings, ellipticallypolarizing coatings, transitional coatings, and protective coatings.Non-limiting examples of such coatings are provided above.

Other non-limiting embodiments disclosed herein provide a compositeoptical element comprising a substrate, an at least partially orderedpolymeric sheet connected to at least a portion of the substrate, and atleast one at least partially aligned photochromic-dichroic compoundconnected to at least a portion of the at least partially orderedpolymeric sheet and having an average absorption ratio greater than 2.3in an activated state as determined according to the CELL METHOD. Forexample, although not limiting herein, according to one non-limitingembodiment a stretched polymer sheet containing at least onephotochromic-dichroic compound that is at least partially aligned by theoriented polymer chains of the stretched polymer sheet can be connectedto at least a portion of the substrate.

Further, according to various non-limiting embodiments, the compositeoptical element can comprise a plurality of polymeric sheets, at leastone of which is at least partially ordered, connected to at least aportion of the substrate. For example, although not limiting herein, thecomposite optical element can comprise a substrate and an at leastpartially ordered polymeric sheet comprising at least one at leastpartially aligned photochromic-dichroic compound that interposed betweento dimensionally stable or “rigid” polymer sheets connected to at leasta portion of the substrate. According to other non-limiting embodiments,the composite optical element can comprise two or more at leastpartially ordered polymeric sheets comprising an at least partiallyaligned photochromic-dichroic compound that are connected to at least aportion of the substrate. Further, the two or more at least partiallyordered polymeric sheets can have the same general direction ordifferent general directions and can comprise the samephotochromic-dichroic compound or different photochromic-dichroiccompounds. Still further, the at least two at least partially orderedpolymeric sheets can be stacked or layered on the substrate or they canbe positioned adjacent each other on the substrate.

Examples of at least partially ordered polymeric sheets that can be usedin conjunction with this non-limiting embodiment include, withoutlimitation, stretched polymer sheets, ordered liquid crystal polymersheets, and photo-oriented polymer sheets. Examples of polymericmaterials, other than liquid crystal materials and photo-orientationmaterials that can be used in forming polymeric sheets according tovarious non-limiting embodiments disclosed herein include withoutlimitation: polyvinyl alcohol, polyvinyl chloride, polyurethane,polyacrylate, and polycaprolactam. Non-limiting examples of methods ofat least partially ordering polymeric sheets are described below in moredetail.

Still other non-limiting embodiments disclosed herein provide acomposite optical element comprising a substrate and at least one sheetconnected to at least a portion of the substrate, the at least one sheetcomprising: an at least partially ordered liquid crystal polymer havingat least a first general direction, at least one at least partiallyordered liquid crystal material having at least a second generaldirection distributed within at least a portion of the liquid crystalpolymer, and at least one photochromic-dichroic compound that is atleast partially aligned with at least a portion of the at least one atleast partially ordered liquid crystal material, wherein at least thesecond general direction is generally parallel to at least the firstgeneral direction.

Non-limiting embodiments of methods of making optical elements anddevices will now be described. One non-limiting embodiment provides amethod of making an optical element comprising forming an at leastpartial coating comprising at least one at least partially alignedphotochromic-dichroic compound on at least a portion of a substrate. Asused herein the term “on” means in direct contact with an object (suchas a substrate) or in indirect contact with the object through one ormore other coatings or structures, at least one of which is in directcontact with the object. Further, according to this non-limitingembodiment, in addition to the at least one at least partially alignedphotochromic-dichroic compound, at least one at least partially orderedanisotropic material can be connected to at least a portion of thesubstrate.

According to this non-limiting embodiment, the at least partial coatingcan have an average absorption ratio of at least 1.5. Further, accordingto this and other non-limiting embodiments of methods of making elementsand devices disclosed herein, the at least one at least partiallyaligned photochromic-dichroic compound can have an average absorptionratio greater than 2.3 in an activated state as determined according tothe CELL METHOD. Non-limiting examples of photochromic-dichroiccompounds that are useful in conjunction with the methods of makingelements and devices disclosed herein are set forth above in detail.

According to various non-limiting embodiments disclosed herein, formingthe at least partial coating comprising the at least one at leastpartially aligned photochromic-dichroic compound can comprise applyingthe at least one photochromic-dichroic compound and at least oneanisotropic material to at least a portion of the substrate, at leastpartially ordering at least a portion of the at least one anisotropicmaterial, and at least partially aligning at least a portion of the atleast one photochromic-dichroic compound with at least a portion of theat least partially ordered anisotropic material. Non-limiting methods ofapplying the at least one photochromic-dichroic compound and the atleast one anisotropic material to the substrate that can be used inconjunction with the methods according to various non-limitingembodiments disclosed herein include, but are not limited to, spincoating, spray coating, spray and spin coating, curtain coating, flowcoating, dip coating, injection molding, casting, roll coating, wirecoating, and overmolding.

According to other non-limiting embodiments, applying the at least onephotochromic-dichroic compound and at least one anisotropic material toat least a portion of the substrate can comprise forming an at leastpartial coating of the anisotropic material on at least a portion of amold, which may be treated with a release material. Thereafter, at leasta portion of the at least one anisotropic material can be at leastpartially ordered (as discussed in more detail below) and at leastpartially set. Thereafter, the substrate can be formed over the at leastpartial coating (i.e., overmolding), for example, by casting thesubstrate forming material in the mold. The substrate forming materialcan then be at least partially set to form the substrate. Subsequently,the substrate and the at least partial coating of the at least partiallyordered anisotropic material can be released from the mold. Further,according to this non-limiting embodiment, the at least onephotochromic-dichroic compound can be applied to the mold with theanisotropic material, or it can be imbibed into the anisotropic materialafter the anisotropic material has been applied to the mold, after theanisotropic material has been at least partially ordered, or after thesubstrate with the at least partial coating of the ordered anisotropicmaterial has been released from the mold.

According to other non-limiting embodiments disclosed herein, formingthe at least partial coating comprising the at least one at leastpartially aligned photochromic-dichroic compound can comprise applyingat least one anisotropic material to at least a portion of thesubstrate, imbibing at least one photochromic-dichroic compound into atleast a portion of the at least one anisotropic material, at leastpartially ordering at least a portion of the at least one anisotropicmaterial, and at least partially aligning at least a portion of the atleast one photochromic-dichroic compound with at least a portion of theat least partially ordered anisotropic material. Non-limiting methods ofimbibing photochromic-dichroic compounds into various coatings aredescribed herein below in more detail.

Non-limiting methods of ordering the anisotropic material includeexposing the anisotropic material to at least one of a magnetic field,an electric field, linearly polarized ultraviolet radiation, linearlypolarized infrared radiation, linearly polarized visible radiation, anda shear force. Further, the at least one anisotropic material can be atleast partially ordered by aligning at least a portion of theanisotropic material with another material or structure. For example,although not limiting herein, the at least one anisotropic material canbe at least partially ordered by aligning the anisotropic material withan orientation facility—such as, but not limited to, those orientationfacilities previously discussed.

As previously described, by ordering at least a portion of the at leastone anisotropic material, it is possible to at least partially align atleast a portion of the at least one photochromic-dichroic compound thatcontained within or otherwise connected to the anisotropic material.Although not required, the at least one photochromic-dichroic compoundcan be at least partially aligned while in an activated state. Further,according to various non-limiting embodiments disclosed herein, applyingthe at least one photochromic-dichroic compound and the at least oneanisotropic material to the portion of the substrate can occur atessentially the same time as, prior to, or after ordering the at leastone anisotropic material and/or aligning the at least onephotochromic-dichroic compound.

For example, according to one non-limiting embodiment applying the atleast one photochromic-dichroic compound and that the at least oneanisotropic material can occur at essentially the same time as orderingat least a portion of the at least one anisotropic material and aligningat least a portion of the at least one photochromic-dichroic compound.More particularly, according to this limiting embodiment, the at leastone photochromic-dichroic compound and at least one anisotropic materialcan be applied to at least a portion of the substrate using a coatingtechnique that can introduce a shear force to at least a portion of theanisotropic material during application such that at least a portion ofthe at least one anisotropic material can be at least partially orderedgenerally parallel to the direction of the applied shear force. Forexample, although not limiting herein, a solution or mixture (optionallyin a solvent or carrier) of the at least one photochromic-dichroiccompound and the at least one anisotropic material can be curtain coatedon to the at least a portion of the substrate such that shear forces areintroduced to the materials being applied due to relative movement ofthe surface of the substrate with respect to the materials beingapplied. The shear forces can cause at least a portion of the at leastone anisotropic material to be ordered in a general direction that isessentially parallel to the direction of the movement of the surface. Asdiscussed above, by ordering at least a portion of the at least oneanisotropic material in this manner, at least a portion of the at leastone photochromic-dichroic compound which is contained within orconnected to the anisotropic material can be aligned by at least aportion of the at least partially ordered anisotropic material. Further,although not required, by exposing at least a portion of the at leastone photochromic-dichroic compound to actinic radiation during thecurtain coating process, such that at least a portion of the at leastone photochromic-dichroic compound is in an activated state, at leastpartial alignment of the at least one photochromic-dichroic compoundwhile in the activated state can be achieved.

In another non-limiting embodiment wherein the at least onephotochromic-dichroic compound and the at least one anisotropic materialare applied to the portion of the substrate prior to ordering at least aportion of the at least one anisotropic material and aligning at least aportion of the at least one photochromic-dichroic compound, applying thematerials can comprise spin coating a solution or mixture of the atleast one photochromic-dichroic compound and at least one anisotropicmaterial (optionally in a solvent or carrier) onto at least a portion ofat least one surface of the substrate. Thereafter, according to thisnon-limiting embodiment, at least a portion of the at least oneanisotropic material can be at least partially ordered, for example, byexposing at least a portion of the at least one anisotropic material toa magnetic field, an electric field, linearly polarized ultravioletradiation, linearly polarized infrared radiation, linearly polarizedvisible radiation, or a shear force. Further at least a portion of theat least one anisotropic material can be at least partially ordered byaligning the at least a portion with another material or structure, forexample, an orientation facility

In still another non-limiting embodiment, wherein at least a portion ofthe at least one photochromic-dichroic compound is at least partiallyaligned and the at least one anisotropic material is at least partiallyordered prior to being applied to at least a portion of the substrate, asolution or mixture (optionally in a solvent or carrier) of the at leastone photochromic-dichroic compound and the at least anisotropic materialcan be applied to an ordered polymeric sheet to form an at least partialcoating. Thereafter, at least a portion of the at least one anisotropicmaterial can be allowed to align with at least a portion of the orderedpolymeric sheet. The polymeric sheet can be subsequently applied to atleast a portion of the substrate by, for example, but not limited to,laminating or bonding. Alternatively, the coating can be transferredfrom the polymeric sheet to the substrate by methods known in the art,such as, but not limited to hot stamping. Other methods of applyingpolymeric sheets are described herein in more detail.

In another non-limiting embodiment, applying the at least onephotochromic-dichroic compound and at least one anisotropic material toat least a portion of the substrate can comprise applying aphase-separating polymer system comprising a matrix phase formingmaterial comprising a liquid crystal material and a guest phase formingmaterial comprising the at least one anisotropic material and at leastone photochromic-dichroic compound. After applying the phase-separatingpolymer system, according to this non-limiting embodiment, at leastportion of the liquid crystal material of matrix phase and at least aportion of the anisotropic material of the guest phase are at leastpartially ordered, such that at least a portion of the at least onephotochromic-dichroic compound is aligned with at least a portion of theat least partially ordered anisotropic material of the guest phase.Non-limiting methods of at least partially ordering at least portion ofthe of the matrix phase forming material and at least a portion of theguest phase forming material of the phase-separating polymer systeminclude exposing at least a portion of the at least partial coatingcomprising the phase-separating polymer system to at least one of: amagnetic field, an electric field, linearly polarized infraredradiation, linearly polarized ultraviolet radiation, linearly polarizedvisible radiation, and a shear force. Further, at least partiallyordering at least a portion of the matrix phase forming material and atleast a portion of the guest phase forming material can comprise atleast partially aligning at the portions with an orientation facility,as described in more detail below.

After at least partially ordering at least a portion of the matrix phaseforming material and the guest phase forming material, at least aportion of the guest phase forming material can be separated from atleast a portion of the matrix phase forming material by at least one ofpolymerization induced phase separation and solvent induced phaseseparation. Although for clarity the separation of the matrix and guestphase forming materials is described herein in relation to the guestphase forming material separating from the matrix phase formingmaterial, it should be appreciated that this language is intended tocover any separation between the two phase forming materials. That is,this language is intended to cover separation of the guest phase formingmaterial from the matrix phase forming material and separation of thematrix phase forming material from the guest phase forming material, aswell as, simultaneous separation of both phase forming materials and anycombination thereof.

According to various non-limiting embodiments disclosed herein, thematrix phase forming material can comprise a liquid crystal materialchosen form liquid crystal monomers, liquid crystal pre-polymers, andliquid crystal polymers. Further, according to various non-limitingembodiments, the guest phase forming material can comprise a liquidcrystal material chosen from liquid crystal mesogens, liquid crystalmonomers, and liquid crystal polymers and pre-polymers. Non-limitingexamples of such materials are set forth in detail above.

In one specific non-limiting embodiment, phase-separating polymer systemcan comprise a mixture of a matrix phase forming material comprising aliquid crystal monomer, a guest phase forming material comprising liquidcrystal mesogens, and at least one photochromic-dichroic compound.According to this non-limiting embodiment, causing at least a portion ofthe guest phase forming material to separate from at least a portion ofthe matrix phase forming material can comprise polymerization inducedphase-separation. That is, at least a portion of the liquid crystalmonomer of the matrix phase can be polymerized and thereby separatedfrom at least a portion of the liquid crystal mesogens of the guestphase forming material. Non-limiting methods of polymerization that canbe used in conjunction with various non-limiting embodiments disclosedherein include photo-induced polymerization and thermally-inducedpolymerization.

In another specific non-limiting embodiment, phase-separating polymersystem can comprise a mixture of a matrix phase forming materialcomprising a liquid crystal monomer, a guest phase forming materialcomprising a low viscosity liquid crystal monomer having a differentfunctionality from the liquid crystal monomer of the matrix phase, andat least one photochromic-dichroic compound. As used herein, the term“low viscosity liquid crystal monomer,” refers to a liquid crystalmonomer mixture or solution that is freely flowing at room temperature.According to this non-limiting embodiment, causing at least a portion ofthe guest phase forming material to separate from at least a portion ofthe matrix phase forming material can comprise polymerization inducedphase-separation. That is, at least a portion of the liquid crystalmonomer of the matrix phase can be polymerized under conditions that donot cause the liquid crystal monomer of the guest phase to polymerize.During polymerization of the matrix phase forming material, the guestphase forming material will separate from the matrix phase formingmaterial. Thereafter, the liquid crystal monomer of the guest phaseforming material can be polymerized in a separate polymerizationprocess.

In another specific non-limiting embodiment, the phase-separatingpolymer system can comprise a solution in at least one common solvent ofa matrix phase forming material comprising a liquid crystal polymer, aguest phase forming material comprising a liquid crystal polymer that isdifferent from the liquid crystal polymer of the matrix phase formingmaterial, and at least one photochromic-dichroic compound. According tothis non-limiting embodiment, causing at least a portion of the guestphase forming material to separate from the matrix phase formingmaterial can comprise solvent induced phase-separation. That is, atleast a portion of the at least one common solvent can be evaporatedfrom the mixture of liquid crystal polymers, thereby causing the twophases to separate from each other.

Alternatively, according to various non-limiting embodiments disclosedherein, forming the at least partial coating comprising the at least oneat least partially aligned photochromic-dichroic compound can compriseapplying at least one anisotropic material to at least a portion of thesubstrate, imbibing the at least one photochromic-dichroic compound intoat least a portion of the at least one anisotropic material, at leastpartially ordering at least a portion of the anisotropic material, andat least partially aligning at least a portion of the at least onephotochromic-dichroic compound with at least a portion of the at leastpartially ordered anisotropic material. Further, although not limitingherein, at least partially ordering at least a portion of theanisotropic material can occur before imbibing the at least onephotochromic-dichroic compound into at least a portion thereof. Stillfurther, although not required, the at least one photochromic-dichroiccompound can be at least partially aligned while in an activated state.Non-limiting methods of applying and aligning anisotropic materials aredescribed herein below.

For example, according to one non-limiting embodiment, the at least onephotochromic-dichroic compound can be imbibed into the anisotropicmaterial, for example, by applying a solution or mixture of the at leastone photochromic-dichroic compound in a carrier to a portion of the atleast anisotropic material and allowing at least a portion of the atleast one photochromic-dichroic compound to diffuse into the anisotropicmaterial, either with or without heating. Further, according to thisnon-limiting embodiment, the anisotropic material can be part of aphase-separated polymer coating as described above.

Other non-limiting embodiments disclosed herein provide a method ofmaking an optical element comprising imparting at least one orientationfacility to at least a portion of a substrate, and subsequently formingan at least partial coating comprising at least one at least partiallyaligned photochromic-dichroic compound on at least a portion of the atleast one orientation facility. According to this and other non-limitingembodiments disclosed herein, imparting the at least one orientationfacility to the at least a portion of a substrate can comprise at leastone of: forming an at least partial coating comprising an at leastpartially ordered alignment medium on at least a portion of thesubstrate, applying an at least partially ordered polymer sheet to theat least a portion of the substrate, at least partially treating atleast a portion of the substrate, and forming a Langmuir-Blodgett filmon at least a portion of the substrate.

According to one non-limiting embodiment, imparting the at least oneorientation facility on the at least a portion of the substrate cancomprise forming an at least partial coating comprising an at leastpartially ordered alignment medium on at least a portion of thesubstrate. Further, according to this non-limiting embodiment, formingthe at least partial coating can comprise applying an alignment mediumto the at least a portion of the substrate and at least partiallyordering at least a portion of the alignment medium. Methods of at leastpartially ordering at least portion of the alignment medium that can beused in conjunction with this and other non-limiting embodimentsdisclosed herein include, but are not limited to, exposing the at leasta portion of the alignment medium to at least one of linearly polarizedultraviolet radiation, linearly polarized infrared radiation, linearlypolarized visible radiation, a magnetic field, an electric field, and ashear force. Further, ordering at least portion of the alignment mediumcan comprise at least partially treating at least a portion of a surfaceof the at least partial coating comprising the alignment medium by, forexample and without limitation, etching or rubbing the at least aportion of the alignment medium.

For example, although not limiting herein, according to one non-limitingembodiment wherein the orientation facility comprises an at leastpartial coating comprising an alignment medium that is aphoto-orientation material (such as, but not limited to aphoto-orientable polymer network), imparting the orientation facilitycan comprise forming an at least partial coating comprising aphoto-orientation material on at least a portion of the substrate, andat least partially ordering at least a portion of the photo-orientationmaterial by exposing the at least a portion to linearly polarizedultraviolet radiation. Thereafter, the at least onephotochromic-dichroic compound can be applied to at least a portion ofthe at least partially ordered photo-orientation material and at leastpartially aligned.

Although not required, according to various non-limiting embodimentswherein imparting the orientation facility comprises forming an at leastpartial coating of an at least partially ordered alignment medium, atleast a portion of the alignment medium can be at least partially set.Further, at least partially setting the at least a portion of thealignment medium can occur at essentially the same time as aligning theat least a portion of the alignment medium or it can occur afteraligning the at least a portion of the alignment medium. Still further,according to various non-limiting embodiments disclosed herein, at leastpartially setting the at least a portion of the alignment medium cancomprise at least partially curing the at least a portion by exposingthe at least a portion of the alignment medium to infrared, ultraviolet,gamma, microwave or electron radiation so as to initiate thepolymerization reaction of the polymerizable components or cross-linkingwith or without a catalyst or initiator. If desired or required, thiscan be followed by a heating step.

As discussed above, according to various non-limiting embodimentsdisclosed herein, subsequent to imparting the orientation facility on atleast a portion of the substrate, an at least partial coating comprisingat least one at least partially aligned photochromic-dichroic compoundis formed on at least a portion of the orientation facility. Methods offorming at least partial coatings comprising at least onephotochromic-dichroic compound that is at least partially aligned on atleast a portion of the at least one orientation facility include thosemethods of forming at least partial coatings comprising at least onephotochromic-dichroic compound that is at least partially aligned on atleast a portion of a substrate that are set forth above in detail.

For example, although not limiting herein, forming the at least partialcoating comprising the at least one at least partially alignedphotochromic-dichroic compound can include, spin coating, spray coating,spray and spin coating, curtain coating, flow coating, dip coating,injection molding, casting, roll coating, wire coating, and overmoldinga composition comprising the photochromic-dichroic compound on to theorientation facility, and thereafter, aligning at least a portion of thephotochromic-dichroic compound with the orientation facility and/or withanother material or structure (such as an alignment transfer material ifpresent), with or without exposure to a magnetic field, an electricfield, linearly polarized infrared radiation, linearly polarizedultraviolet radiation, linearly polarized visible radiation or a shearforce.

According to one non-limiting embodiment, forming the at least partialcoating comprising the at least one photochromic-dichroic compound thatis at least partially aligned on at least a portion of the at least oneorientation facility can comprise applying a polymerizable composition,at least one anisotropic material, and at least onephotochromic-dichroic compound on at least a portion of the at least oneorientation facility. Thereafter, at least a portion of the at least oneanisotropic material can be at least partially aligned with at least aportion of the at least one orientation facility and at least partiallyaligning at least a portion of the at least one photochromic-dichroiccompound with at least a portion of the at least partially alignedanisotropic material. After at least partially aligning at least aportion of the at least one anisotropic material and the at least onephotochromic-dichroic compound, at least a portion of the at leastpartial coating can be subjected to a dual curing process, wherein atleast a portion of the at least one anisotropic material and at least aportion of the polymerizable composition are at least partially setusing at least two curing methods. Non-limiting examples of suitablecuring methods include exposing the at least partial coating toultraviolet radiation, visible radiation, gamma radiation, microwaveradiation, electron radiation, or thermal energy.

For example, although not limiting herein, in one embodiment at least aportion of the anisotropic material can be exposed to ultraviolet orvisible radiation to cause at least a portion of the at least oneanisotropic material to at least partially set. Thereafter, at least aportion of the polymerizable composition can be at least partially setby exposure to thermal energy. Further, although not required, at leasta portion of the at least one photochromic-dichroic compound can be atleast partially aligned with at least a portion of the at least oneanisotropic material while in an activated state by exposing the atleast partial coating to ultraviolet radiation sufficient to cause thephotochromic-dichroic compound to switch from a first state to a secondstate, but insufficient to cause the anisotropic material to at leastpartially set, while the at least one anisotropic material is at leastpartially aligned with at least a portion of the at least oneorientation facility (as discussed above).

In one specific non-limiting embodiment, the polymerizable compositioncan be dihydroxy and isocyanate monomers and the at least oneanisotropic material can comprise a liquid crystal monomer. According tothis non-limiting embodiment, after applying the polymerizablecomposition, the anisotropic material and the at least onephotochromic-dichroic compound on the orientation facility, at least aportion of the anisotropic material can be at least partially alignedwith at least a portion of the at least one orientation facility and theat least one photochromic-dichroic compound can be at least partiallyaligned with the anisotropic material. Further, after alignment, atleast a portion of the coating can be exposed to ultraviolet or visibleradiation sufficient to cause at least a portion the anisotropicmaterial to least partially set. Further, before, during or aftersetting at least a portion of the anisotropic material, at least aportion of the polymerizable composition can be at least partially setby exposing at least a portion of the at least partial coating tothermal energy.

In another non-limiting embodiment, the dual cure process can comprisefirst exposing at least a portion of the polymerizable composition tothermal energy sufficient to cause at least a portion of the atpolymerizable composition to at least partially set. Thereafter, atleast a portion of the at least one anisotropic material can be exposedto ultraviolet or visible radiation to cause at least a portion of theanisotropic material to at least partially set. Further, at least aportion of the at least one anisotropic material can be at leastpartially aligned before, during or after exposing at least a portion ofthe coating to thermal energy and prior to at least partially setting atleast a portion of the at least one anisotropic material.

In still another non-limiting embodiment, the dual cure process cancomprise at least partially setting at least a portion of thepolymerizable composition at essentially the same time as at leastpartially setting at least a portion of the anisotropic material, forexample, by simultaneously exposing the at least partial coating toultraviolet or visible radiation and thermal energy.

Further, as previously discussed in relation to coatings comprisinginterpenetrating polymer networks, according to various non-limitingembodiments disclosed herein, polymerizable composition can be anisotropic material or an anisotropic material, provided that the atleast partial coating comprising the at least one at least partiallyaligned photochromic-dichroic compound is, on the whole, anisotropic.

Additionally, the methods of making optical elements and devicesaccording to various non-limiting embodiments disclosed herein canfurther comprise forming an at least partial primer coating on at leasta portion of the substrate prior to imparting the at least oneorientation facility to the at least a portion of the substrate or priorto forming an at least partial coating comprising the at least one atleast partially aligned photochromic-dichroic compound thereon.Moreover, at least one additional at least partial coating chosen fromphotochromic coatings, anti-reflective coatings, linearly polarizingcoatings, circularly polarizing coatings, elliptically polarizingcoatings, transitional coatings, primer coatings and protective coatingscan be formed on at least a portion of at least one surface of thesubstrate and/or over at least a portion of the at least partial coatingcomprising the least one photochromic-dichroic compound. Non-limitingexamples of suitable primer coatings, photochromic coatings,anti-reflective coatings, linearly polarizing coatings, transitionalcoatings, primer coatings and protective coatings are all describedabove.

Other non-limiting embodiments disclosed herein provide methods ofmaking an optical element comprising forming an at least partial coatingon at least a portion of a substrate and adapting at least a portion ofthe at least partial coating to switch from a first state to a secondlinearly polarizing state in response to actinic radiation and to revertback to the first sate in response to thermal energy. According to onenon-limiting embodiment forming the at least partial coating on at leasta portion of the substrate and adapting the at least a portion of the atleast partial coating to switch from a first state to a second linearlypolarizing state in response to actinic radiation and to revert back tothe first sate in response to thermal energy can occur at essentiallythe same time. According to another non-limiting embodiment, forming theat least partial coating on at least a portion of the substrate occursprior to adapting the at least a portion of the at least partial coatingto switch from a first state to a second linearly polarizing state inresponse to actinic radiation and to revert back to the first sate inresponse to thermal energy. According to still another non-limitingembodiment, forming the at least partial coating on at least a portionof the substrate occurs after adapting the at least a portion of the atleast partial coating to switch from a first state to a second linearlypolarizing state in response to actinic radiation and to revert back tothe first sate in response to thermal energy.

In one non-limiting embodiment, forming the at least partial coating onthe at least a portion of the substrate can comprise applying at leastone anisotropic material and at least one photochromic-dichroic compoundto at least a portion of the substrate, and adapting at least a portionof the at least partial coating to switch from a first state to a secondlinearly polarizing state in response to actinic radiation and to revertback to the first sate in response to thermal energy can comprise atleast partially aligning at least a portion of the at least onephotochromic-dichroic compound. Further, according to this non-limitingembodiment at least partially aligning at least a portion of the atleast one photochromic-dichroic compound can comprise at least partiallyordering at least a portion of the at least one anisotropic material andat least partially aligning the at least one photochromic-dichroiccompound with at least a portion of the at least partially ordered atleast one anisotropic material. Still further, although not required,the at least one photochromic-dichroic compound can be aligned while inan activated state, for example, by exposing the photochromic-dichroiccompound to actinic radiation sufficient to cause thephotochromic-dichroic compound to switch from a first state to a secondstate while aligning the photochromic-dichroic compound.

In another non-limiting embodiment, forming the at least partial coatingon at least a portion of the substrate can comprise applying analignment medium to the at least a portion of the substrate, andadapting at least a portion of the at least partial coating to switchfrom a first state to a second linearly polarizing state in response toactinic radiation and to revert back to the first sate in response tothermal energy can comprise at least partially ordering at least aportion of the alignment medium, applying at least onephotochromic-dichroic compound to at least a portion of the at leastpartial coating comprising the alignment medium, and at least partiallyaligning at least a portion of the at least one photochromic-dichroiccompound.

In one non-limiting embodiment, applying the at least onephotochromic-dichroic compound to at least a portion of the at leastpartial coating comprising the at least partially ordered alignmentmedium can comprise forming an at least partial coating comprising theat least one photochromic-dichroic compound and at least one anisotropicmaterial on at least a portion of the at least partial coatingcomprising the at least partially ordered alignment medium. Moreover, atleast partially aligning at least a portion of the at least onephotochromic-dichroic compound can comprise aligning at least a portionof the at least one anisotropic material with at least a portion of theat least partially ordered alignment medium. Further, although notrequired, at least a portion of the at least partial coating comprisingthe alignment medium can be at least partially set prior to applying theat least one photochromic-dichroic compound.

Additionally or alternatively, the at least one photochromic-dichroiccompound can be applied to at least a portion of the at least partialcoating comprising the at least partially ordered alignment medium byimbibition. Suitable imbibition techniques are described, for example,U.S. Pat. Nos. 5,130,353 and 5,185,390, the specifications of which arespecifically incorporated by reference herein. For example, although notlimiting herein, the photochromic-dichroic compound can be applied to atleast a portion of the at least partial coating comprising the at leastpartially ordered alignment medium by applying the at least onephotochromic-dichroic compound, either as the neat photochromic-dichroiccompound or dissolved in a polymeric or other organic solvent carrier,and allowing the photochromic-dichroic compound to diffuse into at leasta portion of the at least partial coating comprising the at leastpartially ordered alignment medium, either with or with out heating.Further, if desired, the at least one photochromic-dichroic compound canbe exposed to actinic radiation sufficient to cause the at least onephotochromic compound to switch from a first state to a second stateduring diffusion.

Other non-limiting embodiments disclosed herein provide a method ofmaking an optical element comprising forming an at least partial coatingcomprising an alignment medium on at least a portion of at least onesurface of a substrate and at least partially ordering at least aportion of the alignment medium, forming at least one at least partialcoating comprising an alignment transfer material on at least a portionof the at least partial coating comprising the alignment medium and atleast partially aligning at least a portion of the alignment transfermaterial with at least a portion of the at least partially orderedalignment medium, and forming an at least partial coating comprising ananisotropic material and at least one photochromic-dichroic compound onat least a portion of the alignment transfer material, at leastpartially aligning at least a portion of the anisotropic material withat least a portion of the at least partially aligned alignment transfermaterial, and at least partially aligning at least a portion of the atleast one photochromic-dichroic compound with at least a portion of theat least partially aligned anisotropic material.

Further, according to various non-limiting embodiments disclosed herein,forming the at least one at least partial coating comprising thealignment transfer material can comprise forming a first at leastpartial coating comprising an alignment transfer material, the first atleast partial coating having a thickness ranging from 2 to 8 microns, atleast partially aligning at least a portion of the alignment transfermaterial of the first at least partial coating with at least a portionof the at least partially ordered alignment medium, and at leastpartially setting at least a portion of the at least partially orderedalignment transfer material of the first at least partial coating.Thereafter, a second at least partial coating having a thickness rangingfrom greater than 5 to 20 microns and comprising an alignment transfermaterial can be applied to at least a portion of the first at leastpartial coating and at least a portion of the alignment transfermaterial of the second at least partial coating can be at leastpartially aligned with at least a portion of the at least partiallyaligned alignment transfer material of the first at least partialcoating.

Still other non-limiting embodiments disclosed herein provide a methodof making a composite optical element comprising connecting at least oneat least partially ordered polymeric sheet to at least a portion of asubstrate, the at least partially ordered polymeric sheet comprising atleast one at least partially aligned photochromic-dichroic compoundconnected to at least a portion thereof and having an average absorptionratio greater than 2.3 in an activated state as determined according tothe CELL METHOD. Although not limiting herein, according to thisnon-limiting embodiment, the at least one at least partially orderedpolymeric sheet can comprise, for example, a stretched polymer sheet, aphoto-oriented polymer sheet, an at least partially orderedphase-separated polymer sheet, or a combination thereof.

Other non-limiting embodiments disclosed herein provide a method ofmaking a composite optical element comprising connecting a sheetcomprising an at least partially ordered liquid crystal polymer havingat least a first general direction, an at least partially ordered liquidcrystal material distributed within at least a portion of the at leastpartially ordered liquid crystal polymer, and at least onephotochromic-dichroic compound that is at least partially aligned withthe at least partially ordered liquid crystal material to at least aportion of the substrate. Further, according to this non-limitingembodiment, the at least partially ordered liquid crystal materialdistributed within the at least a portion of the at least partiallyordered liquid crystal polymer can have at least a second generaldirection that is generally parallel to at least the first generaldirection of the liquid crystal polymer.

For example, although not limiting herein, according to one non-limitingembodiment, forming the sheet can comprise applying a phase-separatingpolymer system comprising a matrix phase forming material comprising aliquid crystal material, a guest phase forming material comprising aliquid crystal material, and at least one photochromic-dichroic compoundon to at least a portion a substrate. Thereafter, at least a portion ofthe matrix phase forming material and at least a portion of the guestphase forming material can be at least partially ordered, and a least aportion of the at least one photochromic-dichroic compound can be atleast partially aligned with at least a portion of the guest phaseforming material. After alignment, at least a portion of the guest phaseforming material can be separated from at least a portion of the matrixphase forming material by at least one of polymerization inducedphase-separation and solvent induced phase-separation, and the at leastpartially ordered, phase-separated polymer coating can be removed fromthe substrate to form the sheet.

Alternatively, the phase-separating polymer system can be applied on thesubstrate, ordered and aligned as discussed above, and thereafterremoved from the substrate to form a phase-separated polymer sheet.Subsequently, at least one photochromic-dichroic compound can be imbibedinto at least a portion of the sheet. Alternatively or additionally, atleast one photochromic-dichroic compound can be imbibed into the coatingprior to removing the coating from the substrate to form the sheet.

According to still another non-limiting embodiment forming the sheet cancomprise: forming an at least partially ordered liquid crystal polymersheet and imbibing liquid crystal mesogens and at least onephotochromic-dichroic compound into at least a portion of the at leastpartially ordered liquid crystal polymer sheet. For example, accordingto this non-limiting embodiment, a sheet comprising a liquid crystalpolymer can be formed and at least partially ordered by a method offorming a polymer sheet that can at least partially order the liquidcrystal polymer during formation, for example by extrusion.Alternatively, a liquid crystal polymer can be cast onto a substrate andat least partially ordered by one of the non-limiting methods of atleast partially ordering liquid crystal materials set forth above. Forexample, although not limiting herein, at least a portion of the liquidcrystal material can be exposed to a magnetic or an electric field.After being at least partially ordered, the liquid crystal polymer canbe at least partially set and removed from the substrate to form a sheetcomprising an at least partially ordered liquid crystal polymer matrix.Still further, a liquid crystal polymer sheet can be cast, at leastpartially set, and subsequently stretched to form sheet comprising an atleast partially ordered liquid crystal polymer.

After forming the sheet comprising the at least partially ordered liquidcrystal polymer, at least one liquid crystal mesogen and at least onephotochromic-dichroic compound can be imbibed into at least a portion ofthe liquid crystal polymer matrix. For example, although not limitingherein, the at least one liquid crystal mesogen and the at least onephotochromic-dichroic compound can be imbibed into at least a portion ofthe liquid crystal polymer by applying a solution or mixture of the thatleast one liquid crystal mesogen and the at least onephotochromic-dichroic compound in a carrier to a portion of the liquidcrystal polymer and, thereafter, allowing at least a portion of the atleast one liquid crystal mesogen and the at least onephotochromic-dichroic compound to diffuse into the liquid crystalpolymer sheet, either with or without heating. Alternatively, the sheetcomprising the liquid crystal polymer can be immersed into a solution ormixture of the at least one liquid crystal mesogen and the at least onephotochromic-dichroic compound in a carrier and the at least one liquidcrystal mesogen and the at least one photochromic-dichroic compound canbe imbibed into the liquid crystal polymer sheet by diffusion, eitherwith or without heating.

According to still another non-limiting embodiment, forming the sheetcan comprise forming a liquid crystal polymer sheet, imbibing at least aportion of the liquid crystal polymer sheet with at least one liquidcrystal mesogen and at least one photochromic-dichroic compound (forexample as discussed above), and thereafter at least partially orderingat least a portion of the liquid crystal polymer, at least a portion ofthe at least one liquid crystal mesogen, and the at least onephotochromic-dichroic compound distributed therein. Although notlimiting herein, for example, at least a portion of the liquid crystalpolymer sheet, at least a portion of the at least one liquid crystalmesogen, and at least a portion of the at least onephotochromic-dichroic compound distributed therein can be at leastpartially ordered by stretching the liquid crystal polymer sheet.Further according to this non-limiting embodiment, the liquid crystalpolymer sheet can be formed using conventional polymer processingtechniques, such as, but not limited to, extrusion and casting.

In still another non-limiting embodiment, a photo-oriented polymer sheetcomprising an at least partial coating of an anisotropic material and atleast one photochromic-dichroic compound is applied to the substrate.For example, according to this non-limiting embodiment, photo-orientedpolymer sheet can be formed by applying an at least partial layer of aphoto-orientable polymer network on a release layer and subsequentlyordering and at least partially curing at least a portion of thephoto-orientable polymer network; forming an at least partial coating ofan anisotropic material and at least one photochromic-dichroic compoundon at least a portion of at least partial layer comprising thephoto-orientable polymer network, at least partially aligning at least aportion of the anisotropic material and the at least onephotochromic-dichroic compound with at least a portion of thephoto-orientable polymer network, and at least partially curing at leasta portion of the anisotropic material. The release layer can then beremoved and the at least partial layer of the photo-orientable polymernetwork comprising the at least partial coating of the anisotropicmaterial and the at least one photohcormic-dichroic compound from therelease layer to form the at least partially ordered polymeric sheet.

Further, according to various non-limiting embodiments disclosed herein,connecting the polymeric sheet comprising the at least one at leastpartially aligned photochromic-dichroic compound to at least a portionof the substrate can comprise, for example, at least one of: laminating,fusing, in-mold casting, and adhesively bonding the polymeric sheet tothe at least a portion of the substrate. As used herein, the in-moldcasting includes a variety of casting techniques, such as but notlimited to: overmolding, wherein the sheet is placed in a mold and thesubstrate is formed (for example by casting) over at least a portion ofthe sheet; and injection molding, wherein the substrate is formed aroundthe sheet. According to one non-limiting embodiment, the polymeric sheetcan be laminated on a surface of a first portion of the substrate, andthe first portion of the substrate can be placed in a mold. Thereafter,a second portion of the substrate can be formed (for example by casting)on top of the first portion of the substrate such that the polymericlayer is between the two portions of the substrate.

Another specific non-limiting embodiment provides a method of making anoptical element comprising overmolding an at least partial coatingcomprising an at least partially ordered liquid crystal material and atleast one at least partially aligned photochromic-dichroic compound onat least a portion of an optical substrate, and more particularly, on atleast a portion of an ophthalmic substrate. Referring now to FIG. 2,according to this non-limiting embodiment, the method comprises placingat least portion of a surface 210 of an optical substrate 212 adjacent ato a surface 214 of a transparent mold 216 to define a molding region217. The surface 214 of transparent mold 216 can be concave orspherically negative (as shown), or it can have other configuration asrequired. Further, although not required, a gasket or spacer 215 can beplaced between optical substrate 212 and transparent mold 216. Afterpositioning the optical substrate 212, a liquid crystal material 218containing at least one photochromic-dichroic compound (not shown) canbe introduced into the molding region 217 defined by the surface 210 ofthe optical substrate 212 and the surface 214 of the transparent mold216, such that at least a portion of the liquid crystal material 218 iscaused to flow therebetween. Thereafter, at least a portion of theliquid crystal material 218 can be at least partially ordered, forexample, by exposure to an electric field, a magnetic field, linearlypolarized infrared radiation, linearly polarized ultraviolet radiation,and/or linearly polarized visible radiation, and at least a portion ofthe at least one photochromic-dichroic compound can be at leastpartially aligned with at least a portion of the at least partiallyordered liquid crystal material. Thereafter, the liquid crystal materialcan be at least partially polymerized. After polymerization, the opticalsubstrate having the at least partial coating comprising an at leastpartially ordered liquid crystal material and the at least one at leastpartially aligned photochromic-dichroic compound on at least a portionof a surface thereof can be released from the mold.

Alternatively, the liquid crystal material 218 containing the at leastone photochromic-dichroic compound can be introduced onto surface 214 oftransparent mold 216 prior to placing at least a portion of surface 210of the optical substrate 212 adjacent thereto such that at least aportion of surface 210 contacts at least a portion of the liquid crystalmaterial 218, thereby causing the liquid crystal material 218 to flowbetween surface 210 and surface 214. Thereafter, the liquid crystalmaterial 218 can be at least partially ordered, and at least a portionof the at least one photochromic-dichroic compound can be at leastpartially aligned as discussed above. After polymerization of at least aportion of the liquid crystal material, the optical substrate having theat least partial coating comprising an at least partially ordered liquidcrystal material and the at least one at least partially alignedphotochromic-dichroic compound on at least a portion of a surfacethereof can be released from the mold.

According to still other non-limiting embodiments, an at least partialcoating comprising at least partially ordered liquid crystal material,without the photochromic-dichroic compound, can be formed on the surfaceof an optical substrate as discussed above. After releasing thesubstrate and the coating from the mold, at least onephotochromic-dichroic compound can be imbibed into the at leastpartially ordered liquid crystal material.

Although not shown in FIG. 2, additionally or alternatively, anorientation facility having at least a first general direction can beimparted onto at least a portion of the surface of the transparent moldprior to introducing the liquid crystal material into the mold and/oronto at least a portion of the surface of the optical substrate priorcontacting the surface of the optical substrate with the liquid crystalmaterial. Further, according to this non-limiting embodiment, at leastpartially ordering at least a portion of the liquid crystal material cancomprise at least partially aligning at least a portion of the liquidcrystal material with at least a portion of the at least one orientationfacility on the surface of the mold and/or at least a portion of the atleast one orientation facility on the surface of the optical substrate.

Although not limiting herein, it is contemplated that the aforementionedover molding methods of making at least partial coatings can beparticularly useful in forming coatings on multi-focal ophthalmiclenses, or for forming at least partial coatings for other applicationswhere relatively thick alignment facilities are desired.

As previously discussed, various non-limiting embodiments disclosedherein relate to display elements and devices. Further, as previouslydiscussed, as used herein the term “display” means the visiblerepresentation of information in words, numbers, symbols, designs ordrawings. Non-limiting examples of display elements and devices includescreens, monitors, and security elements. Non-limiting examples ofsecurity elements include security marks and authentication marks thatare connected to at least a portion of a substrate, such as and withoutlimitation: access cards and passes, e.g., tickets, badges,identification or membership cards, debit cards etc.; negotiableinstruments and non-negotiable instruments, e.g., drafts, checks, bonds,notes, certificates of deposit, stock certificates, etc.; governmentdocuments, e.g., currency, licenses, identification cards, benefitcards, visas, passports, official certificates, deeds etc.; consumergoods, e.g., software, compact discs (“CDs”), digital-video discs(“DVDs”), appliances, consumer electronics, sporting goods, cars, etc.;credit cards; and merchandise tags, labels and packaging.

For example, in one non-limiting embodiment, the display element is asecurity element connected to at least a portion of a substrate.According to this non-limiting embodiment the security element comprisesan at least partial coating having a first state and a second state, andbeing adapted to switch from a first state to a second state in responseto at least actinic radiation, to revert back to the first state inresponse to thermal energy, and to linearly polarize at leasttransmitted radiation in at least one of the first state and the secondstate. Non-limiting examples of at least partial coatings adapted toswitch from a first state to a second state in response to at leastactinic radiation, to revert back to the first state in response tothermal energy, and to linearly polarize at least transmitted radiationin at least one of the first state and the second state and methods ofmaking the same are set forth above in detail.

According to this non-limiting embodiment, the security element can be asecurity mark and/or an authentication mark. Further, the securityelement can be connected to at least a portion of a substrate chosenfrom a transparent substrate and a reflective substrate. Alternatively,according to certain non-limiting embodiments wherein a reflectivesubstrate is required, if the substrate is not reflective orsufficiently reflective for the intended application, a reflectivematerial can be first applied to at least a portion of the substratebefore the security mark is applied thereto. For example, a reflectivealuminum coating can be applied to the at least a portion of thesubstrate prior to forming the security element thereon. Still further,security element can be connected to at least a portion of a substratechosen from untinted substrates, tinted substrates, photochromicsubstrates, tinted-photochromic substrates, linearly polarizingsubstrates, circularly polarizing substrates, and ellipticallypolarizing substrates.

Additionally, the at least partial coatings according to theaforementioned non-limiting embodiment can comprise at least onephotochromic-dichroic compound having an average absorption ratio of atleast 1.5 in an activated state as determined according to the CELLMETHOD. According to other non-limiting embodiments disclosed herein,the at least one photochromic-dichroic compound can have an averageabsorption ratio greater than 2.3 in an activated state as determinedaccording to the CELL METHOD. According to still other non-limitingembodiments, the at least one at least partially alignedphotochromic-dichroic compound can have an average absorption ratioranging from 1.5 to 50 in an activated state as determined according tothe CELL METHOD. According to other non-limiting embodiments, the atleast one at least partially aligned photochromic-dichroic compound canhave an average absorption ratio ranging from 4 to 20, can furtherhaving an average absorption ratio ranging from 3 to 30, and can stillfurther having an average absorption ratio ranging from 2.5 to 50 in anactivated state as determined according to the CELL METHOD. However,generally speaking, the average absorption ratio of the at least one atleast partially aligned photochromic-dichroic compound can be anyaverage absorption ratio that is sufficient to impart the desiredproperties to the device or element. Non-limiting examples ofphotochromic-dichroic compounds that are suitable for use in conjunctionwith this non-limiting embodiment are set forth above in detail.

Furthermore, the security elements according to the aforementionednon-limiting embodiment can further comprise one or more other coatingsor sheets to form a multi-layer reflective security element with viewingangle dependent characteristics as described in U.S. Pat. No. 6,641,874,which is hereby specifically incorporated by reference herein. Forexample, one non-limiting embodiment provides a security elementconnected to at least a portion of a substrate comprising an at leastpartial coating having a first state and a second state, and beingadapted to switch from a first state to a second state in response to atleast actinic radiation, to revert back to the first state in responseto thermal energy, and to linearly polarize at least transmittedradiation in at least one of the first state and the second state on atleast a portion of the substrate; and at least one additional at leastpartial coating or sheet chosen from polarizing coatings or sheets,photochromic coatings or sheets, reflective coatings or sheets, tintedcoatings or sheets, circularly polarizing coatings or sheets, retardercoatings or sheets (i.e., coatings or sheets that delay or retard thepropagation radiation therethrough), and wide-angle view coatings orsheets (i.e., coatings or sheets than enhancing viewing angle). Further,according to this non-limiting embodiment, the at least one additionalat least partial coating or sheet can be positioned over the at leastpartial coating having the first state and the second state, under thisleast partial coating, or multiple coating and/or sheets can bepositioned over and/or under this coating.

Other non-limiting embodiments provide a liquid crystal cell, which maybe a display element or device, comprising a first substrate having afirst surface and a second substrate having a second surface, whereinthe second surface of the second substrate is opposite and spaced apartfrom the first surface of the first substrate so as to define an openregion. Further, according to this non-limiting embodiment, a liquidcrystal material adapted to be at least partially ordered and at leastone photochromic-dichroic compound adapted to be at least partiallyaligned and having an average absorption ratio of at least 1.5 in theactivated state as determined according to the CELL METHOD positionedwithin the open region defined by the first surface and the secondsurface to form the liquid crystal cell.

Further according to this non-limiting embodiment, the first substrateand the second substrate can be independently chosen from untintedsubstrates, tinted substrates, photochromic substrates,tinted-photochromic substrates, and linearly polarizing substrates.

The liquid crystal cells according to various non-limiting embodimentsdisclosed herein can further comprise a first orientation facilitypositioned adjacent the first surface and a second orientation facilitypositioned adjacent the second surface. As previously discussed, it ispossible to align a liquid crystal material with an oriented surface.Thus, according to this non-limiting embodiment, at least a portion ofthe liquid crystal material of the liquid crystal cell can be at leastpartially aligned with at least a portion of the first and secondorientation facilities.

Still further, a first electrode can be positioned adjacent at least aportion of the first surface, a second electrode can be positionedadjacent at least a portion of the second surface, and the liquidcrystal cell can form at least a portion of an electrical circuit.Further, if an orientation facility is present (as discussed above), theelectrode can be interposed between the orientation facility and thesurface of the substrate.

Additionally, the liquid crystal cells according to various non-limitingembodiments disclosed herein can further comprise an at least partialcoating or sheet chosen from linearly polarizing coatings or sheets,photochromic coatings or sheets, reflective coatings or sheets, tintedcoatings or sheets, circularly polarizing coatings or sheets,elliptically polarizing coating or sheets, retarder coatings or sheets,and wide-angle view coatings or sheets connected to at least a portionof a surface of at least one of the first substrate and the secondsubstrate.

Other non-limiting embodiments disclosed herein provide an opticalelement comprising a substrate and an at least partial coating having afirst state and a second state on at least a portion of the substrate,the at least partial coating comprising a chiral nematic or cholestericliquid crystal material having molecules that are helically arrangedthrough the thickness of the at least partial coating; and at least onephotohchromic-dichroic compound that is at least partially aligned withthe liquid crystal material such that the long axis of the molecules ofthe photochromic-dichroic compound are generally parallel to themolecules of the liquid crystal material. According to this non-limitingembodiment, the at least partial coating can be adapted to be circularlypolarizing or elliptically polarizing in at least one state.

Various non-limiting embodiments disclosed herein will now beillustrated in the following non-limiting examples.

EXAMPLES Example 1

Sample substrates having a coating comprising an aligned anisotropicmaterial and a photochromic-dichroic compound that was at leastpartially aligned in the activated state connected thereto were preparedas follows. A comparative substrate having a coating comprising analigned anisotropic material and a commercially available photochromicdye that was at least partially aligned in the activated state connectedthereto was also prepared as follows.

Part A: Preparation of Solutions of Anisotropic Materials

Each of the liquid crystal monomers listed in Table I were added to abeaker in the order listed with stirring:

TABLE I Liquid Crystal Monomer Amount (g) RM 23¹ 3.25 RM 257² 3.25 RM82³ 3.25 RM 105⁴ 3.25 ¹RM 23 is a liquid crystal monomer (LCM) availablefrom EMD Chemicals, Inc and is reported to have the molecular formula ofC₂₃H₂₃NO₅. ²RM 257 is a liquid crystal monomer (LCM) available from EMDChemicals, Inc and is reported to have the molecular formula ofC₃₃H₃₂O₁₀ ³RM 82 is a liquid crystal monomer (LCM) available from EMDChemicals, Inc and is reported to have the molecular formula ofC₃₉H₄₄O₁₀. ⁴RM 105 is a liquid crystal monomer (LCM) available from EMDChemicals, Inc and is reported to have the molecular formula ofC₂₃H₂₆O₆.

Anisole (7.0 grams) was then added to the beaker and the resultingmixture was heated to 60° C. and stirred until the solids were dissolvedas determined by visual observation. The resulting liquid crystalmonomer solution (LCMS) had 65 percent solids.

Part B: Preparation of Photochromic-Dichroic Compounds

The following three (3) photochromic-dichroic compounds (P/D-1, P/D-2,and P/D-3, respectively) were prepared as follows.

P/D-1

Step 1

1-phenyl-1-(4-phenylpiperazin-1-yl)phenyl)-prop-2-yn-1-ol (15.8 g, 49.4mmol), 2,3-dimethoxy-7,7-dimethyl-7H-benzo[c]fluoren-5-ol (17.4 g, 54.3mmol) and chloroform (400 mL) were added to a 1000 mL flask equippedwith a dropping funnel and stirred at room temperature. A chloroformsolution of trifluoroacetic acid (0.5 g, 4.4 mmol, in 20 mL chloroform)was added dropwise to the reaction flask via the dropping funnel. A graycolor was obtained after the addition. The resulting reaction mixturewas refluxed for 6 hours and then was stirred overnight at roomtemperature. The chloroform solution was washed with a saturated sodiumbicarbonate water solution, dried over magnesium sulfate andconcentrated. The product was recrystallized from CHCl₃/ethyl ether. Anoff-white solid (26.3 g, yield 91%) was obtained. An NMR spectrum showedthat the product had a structure consistent with3-phenyl-3-(4-(4-phenyl-piperazin-1-yl)phenyl)-13,13-dimethyl-6,7-dimethoxy-indeno[2′,3′:3,4]naphtho[1,2-b]pyran.

Step 2

Under a nitrogen atmosphere at room temperature,3-phenyl-3-(4-(4-phenyl-piperazin-1-yl)phenyl)-13,13-dimethyl-6,7-dimethoxy-indeno[2′,3′:3,4]naphtho[1,2-b]pyranfrom Step 1 (12 g, 17.9 mmol), 1-(4-hydroxyphenyl)piperazine (9.56 g,53.7 mmol) and THF (200 mL) were added to a 1 liter flask equipped witha dropping funnel and stirred. A 1.6 M solution of methyl lithium inethyl ether (67 mL) was added slowly and carefully via the droppingfunnel. An ice bath was used occasionally when the mixture started toboil. During and after the addition of methyl lithium, a large quantityof precipitate was produced within the flask. Thirty minutes after theaddition of methyl lithium, the reaction mixture was poured into a 4 Lbeaker containing 3 L of ice water. The basic mixture was acidified to apH value of about 4 by the addition of 3 N HCl. The precipitate formedwas collected by vacuum filtration, dissolved in chloroform, dried overmagnesium sulfate, concentrated and flash chromatographed. A gray solid(12.6 g, yield 86%) was obtained as the product. An NMR spectrum showedthat the resulting product had a structure consistent with3-phenyl-3-(4-(4-phenyl-piperazin-1-yl)phenyl)-13,13-dimethyl-6-methoxy-7-(4-(4-hydroxyphenyl)-piperazin-1-yl)-indeno[2′,3′:3,4]naphtho[1,2-b]pyran.

Step 3

3-phenyl-3-(4-(4-phenyl-piperazin-1-yl)phenyl)-13,13-dimethyl-6-methoxy-7-(4-(4-hydroxyphenyl)-piperazin-1-yl)-indeno[2′,3′:3,4]naphtho[1,2-b]pyranfrom Step 2 (0.67 g, 0.82 mmol), 4-n-octyloxybiphenyl-4′-carboxylic acid(0.296 g, 0.9 mmol), dicyclohexyl carbodiimide (0.19 g, 1 mmol),4-(dimethylamino)-pyridine (0.01 g, 0.08 mmol) and dichloromethane (10mL) were added to a flask and stirred at room temperature for 24 hours.The solid produced was removed by filtration and the remaining solutionwas concentrated. The resulting solid crude product was purified byflash chromatography (2/8 ethyl acetate/hexanes, volume ratio). Therecovered solid was further purified by dissolution in CHCl₃ andprecipitation from methanol yield a grayish purple solid (0.81 g, yield88%).

An NMR spectrum showed that the final product had a structure consistentwith3-phenyl-3-(4-(4-phenylpiperazin-1-yl)phenyl)-13,13-dimethyl-6-methoxy-7-(4-(4-(4′-octyloxy-biphenyl-4-carbonyloxy)phenyl)piperazin-1-yl)indeno[2′,3′:3,4]naphtho[1,2-b]pyran.

P/D-2

Step 1

4-Hydroxybenzoic acid (45 g, 0.326 mol), dodecylbenzenesulfonic acid (2drops) and ethyl ether (500 mL) were added to a flask and stirred atroom temperature. Neat dihydropyran (DHP)(35 mL, 0.39 mol) was addeddropwise via a dropping funnel within a 30 minute interval and a whitecrystalline precipitate formed. The resulting suspension was stirredovernight and the precipitate was collected by vacuum filtration. Awhite solid product (41 g) was recovered. An NMR spectrum showed thatthe resulting product had a structure consistent with4-(2-tetrahydro-2H-pyranoxy)benzoic acid.

Step 2

The procedure set forth above for P/D-1 was used except that the productof Step 1 (above) was used in place of4-n-octyloxybiphenyl-4′-carboxylic acid in Step 3 of the procedure forP/D-1, and flash chromatography on silica gel was not used for theproduct purification. Instead, the product was purified by a techniqueof dissolution in chloroform followed by precipitation from methanol. AnNMR spectrum showed that the resulting product, a black solid, had astructure consistent with3-phenyl-3-(4-(4-phenyl-piperazin-1-yl)phenyl)-13,13-dimethyl-6-methoxy-7-(4-(4-(4-(2-tetrahydro-2H-pyranoxy)benzoyloxy)phenyl)piperazin-1-yl)indeno[2′,3′:3,4]naphtho[1,2-b]pyran.

Step 3

The product of Step 2 (11 g), pyridinium p-toluenesulfonate (0.27 g),ethyl acetate (250 mL) and methanol (40 mL) were added to a reactionflask and refluxed for 24 hours. The resulting reaction mixture wasextracted with water, dried over magnesium sulfate, concentrated andflash-chromatographed using 3/7 (volume/volume) ethyl acetate/hexane asthe eluant. The recovered solid was added to a flask containingchloroform (50 mL) and stirred for 30 minutes and then precipitated frommethanol (8.32 g).

Step 4

The product of Step 3 (1 g, 1.1 mmol), 2-fluorobenzoyl chloride (0.5 g,3.2 mmol) and pyridine (20 mL) were added to a reaction flask andstirred at room temperature for 4 hours. The resulting mixture waspoured into a beaker containing 300 mL of water. The resultingprecipitate was collected by vacuum filtration, dissolved in chloroform,dried over magnesium sulfate, concentrated and flash-chromatographedfrom silica gel using as an eluant: 2/8 (volume/volume) ethylacetate/hexanes. The recovered solid was further purified by dissolutionin CHCl₃ and precipitation from methanol to yield a gray solid (0.99 g).

An NMR spectrum showed that the final product, a purple solid, had astructure consistent with3-phenyl-3-(4-(4-phenyl-piperazin-1-yl)phenyl)-13,13-dimethyl-6-methoxy-7-(4-(4-(4-(2-fluorobenzoyloxy)benzoyloxy)phenyl)piperazin-1-yl)indeno[2′,3′:3,4]naphtho[1,2-b]pyran.

P/D-3

Step 1

4-Hydroxypiperidine (19.5 g, 0.193 mol),2,3-dimethoxy-7,7-dimethyl-7H-benzo[c]fluoren-5-ol (41.17 g, 0.128 mol)and THF (300 mL) were added to a 2 liter round-bottomed flask equippedwith a bubbler and stirred magnetically at room temperature. A solutionof 3 M methyl Grignard in THF (171 mL, 0.514 mmol) was added to themixture slowly via a dropping funnel under a nitrogen atmosphere. Theresulting mixture was concentrated to a viscous oil. The viscous oil wasmaintained under reflux and stirred for 5 days. Thin layerchromatography showed that 2 products were present in the reaction. Theresulting reaction mixture was poured into a beaker containing water(1000 mL), neutralized with HCl (3 N) to a pH value of 4-6, extractedwith ethyl acetate and flash-chromatographed using 2:8 (volume:volume)ethyl acetate:hexanes as the eluant. Both products were collected andobtained as white solids. An NMR spectrum showed that the major producthad a structure consistent with7,7-dimethyl-3-methoxy-7H-benzo[c]fluorene-2,5-diol and the minorproduct had a structure consistent with7,7-dimethyl-3-methoxy-3-(4-hydroxypiperadin-1-yl)-7H-benzo[c]fluorene-5-ol.

Step 2

7,7-Dimethyl-3-methoxy-7H-benzo[c]fluorene-2,5-diol from Step 1 (5.1 g),1-phenyl-1-(4-pyrrolidin-1-yl-phenyl)-prop-2-yn-1-ol (5.1 g), pyridiniump-toluenesulfonate (0.2 g), trimethyl orthoformate (4 g) and chloroform(100 mL) were added to a reaction flask and stirred at room temperatureover the weekend. The reaction mixture was then concentrated andflash-chromatographed using 2:8 (volume:volume) ethyl acetate:hexanes asthe eluant. A gray solid (9.1 g) was recovered. An NMR spectrum showedthat the resulting product had a structure consistent with3-phenyl-3-(4-(pyrrolidin-1-yl)phenyl)-13,13-dimethyl-6-methoxy-7-hydroxy-indeno[2′,3′:3,4]naphtho[1,2-b]pyran.

Step 3

The procedure of P/D-1 Step 3 was used, except that: the product of Step2 (above) was used instead of the product of Step 2 of P/D-1; the4-(2-tetrahydro-2H-pyranoxy)benzoic acid (of P/D-2 Step 1) was used inplace of 4-n-octyloxybiphenyl-4′-carboxylic acid; and flashchromatography on silica gel was not used for the product purification.Instead, the product was purified by a technique of dissolution inchloroform followed by precipitation from methanol.

Step 4

The procedures of P/D-2 Steps 3 and 4 were followed, in sequence, usingthe product of Step 3 (above). An NMR spectrum showed that the finalproduct, a blue solid, had a structure consistent with3-phenyl-3-(4-(pyrrolidin-1-yl)phenyl)-13,13-dimethyl-6-methoxy-7-(4-(4-hexylbenzoyloxy)benzoyloxy)-indeno[2′,3′:3,4]naphtho[1,2-b]pyran.

Part C: Preparation of Coatings Compositions

After preparation, each of the photochromic-dichroic compounds (P/D-1 toP/D-3) was used to prepare a coating composition (indicated in Table IIbelow as Coating Nos. 1 to 3, which correspond to P/D-1 to P/D-3,respectively) containing a photochromic-dichroic compound and the LCMSfrom Part A as described below. In addition, a coating composition(indicated in Table 1 as Coating No. 4) was prepared using Photosol0265, which is commercially available from PPG Industries and reportedto be 1,3,3,4,5 (or1,3,3,5,6)-pentamethyl-spiro[indoline-2,3-[3H]naphth[2,1-b][1,4]oxazine,and the LCMS from Part A.

Each coating composition was prepared by adding an amount of thephotochromic-dichroic compound to the LCMS prepared in Part A requiredto result in a coating composition having, in percent by weight based onthe total solids of the coating solution: 4.0 percent of thephotochromic-dichroic compound; 1.0 percent of Irgacure 819, aphotoinitiator available from Ciba-Geigy Corporation; 1.0 percent ofTINUVIN-144, a light stabilizer for coatings from Ciba-Geigy; and 0.5percent of the surfactant sold as BYK®-346 additive by BYK Chemie, USA.

Part D: Preparation of Coated Substrates by Alignment with OrientationFacility

Step 1

Ten (10) square test substrates measuring 2″×2″×0.25″ (5.08 cm×5.08cm×0.635 cm) each of which were prepared from either CR-39® monomer orTRIVEX™ brand lens material (both of which are available from PPGIndustries, Inc.). These test substrates are indicated as SubstrateSample Nos. 1x-10x in Table II, wherein x=“A” for substrates made fromCR-39® monomer and x=“B” for substrates made from a TRIVEX™ brand lensmaterial. One test substrate (designated Substrate Sample No. 11 C) wasa 1.5 mm×76 mm diameter plano, GENTEX™ polycarbonate lens (which isavailable from Gentex Optics). All of the aforementioned substrates werewashed using liquid soap and water, rinsed with deionized water, andsubsequently rinsed with isopropyl alcohol. Two (2) of test substrates(labeled Substrate Sample Nos. 9A & 10A in Table II) that were used inthe magnetic alignment procedure described below in Part E were furthercleaned in an ultrasonic bath with 12.5 weight percent sodium hydroxidefor 30 minutes and rinsed with deionized water. All of the cleanedsubstrates were dried and treated with oxygen plasma at a flow rate of100 milliliters (mL) per minute of oxygen at 100 watts of power for oneminute.

Substrate Sample Nos. 9A & 10A were also treated with the adhesive layerforming composition of U.S. Pat. No. 6,150,430 by application of theadhesive layer forming composition for 10 seconds to the substratesspinning at 1500 rpm. After application, the adhesive layer formingcomposition was cured in a Light-Welder® 5000-EC UV light source fromDymax Corp., at a distance of 4 inches from the light for 10 seconds.The test substrates treated in this manner are identified as (Magnetic)in Table 1.

Step 2

After preparation according to Step 1, an orientation facility wasformed on at least a portion of a surface of each of Substrate SampleNos. 1x-8x, and 11C, as follows. A solution of a photo-orientablepolymer network available as Staralign™ 2200 CP4 solution from HuntsmanAdvanced Materials, which designation is reported to mean 4 weightpercent in cyclopentane, was dispensed for 2 to 3 seconds onto each ofthe test substrates indicated above. As the Staralign™ solution wasdispensed onto the substrates, Substrate Sample Nos. 1x-8x were spun at800 revolutions per minute for about 2 to 3 minutes, while SubstrateSample No. 11C was spun at 500 revolutions per minute for 3 minutes.Afterwards, each of the substrates was placed in an oven maintained at130° C. for 20 to 30 minutes.

After applying the photo-orientable polymer network to Substrate SampleNos. 1x-8x and 11C, at least a portion of the photo-orientable polymernetwork was at least partially ordered by exposure to linearly polarizedultraviolet light for 1 minute for Substrate Sample No. 11C, and 2minutes for all of the other substrates, at a peak intensity of 18milliWatts/cm² of UVA (320-390 nm) as measured using a UV Power Puck™electro-optic radiometers from Electronic Instrumentation andTechnology, Inc. The source of ultraviolet light was a BLAK-RAY ModelB-100A Longwave UV Lamp. After ordering at least a portion of thephoto-orientable polymer network, the substrates were cooled to roomtemperature and kept covered.

Step 3

Sample Coating Nos. 14 were then formed on Substrate Sample Nos. 1x-8x,11C, prepared in Steps 1 and 2 of Part D (above) using one of thecoating composition prepared above in Part C as follows. To form each ofthe coatings, the appropriate coating composition was applied to atleast a portion of the orientation facility on the surface of one of thesubstrates (as indicated in Table II) by spincoating. More specifically,approximately 1 mL of the coating composition was dispensed onto atleast a portion of the orientation facility as the substrate, and anyexcess was drained off prior to spinning at 500 revolutions per minutefor 3 minutes for all of the substrate samples, except Substrate SampleNo. 11C, which was spun at 300 to 400 revolutions per minute for 4 to 6minutes. After applying the coating composition, the substrate wasplaced in a 55° C. oven for 20 to 50 minutes to permit at least aportion of the liquid crystal material and at least a portion of thephotochromic-dichroic compound to align.

After alignment, the at least partial coating was tested for alignmentusing two cross-polarized films (#45669) from Edmund Industrial Opticsas follows. The coated substrate was positioned between thecross-polarized films so that the coated substrate was parallel with atleast one of the films. Visible light transmitted through thisorientation is reduced. At least partial alignment was verified byobserving an increase in the transmitted visible light when one of thepolarizing films was rotated 45 degrees clockwise or counterclockwisewhile viewing a visible light source through this configuration.

After verifying at least partial alignment, each of the at least partialcoatings was cured by covering the coated substrate with a cut-offfilter to screen out the ultraviolet wavelengths less than 390nanometers such that the cut-off filter was about 1 mm above the surfaceof the coated substrate. The resulting assembly was placed on anultraviolet conveyor curing line (obtained from Eye Ultraviolet, Inc)and conveyed at three feet per minute beneath two ultraviolet “type D”400 watt/inch iron iodide doped mercury lamps of 10 inches in length,one positioned 2.5 inches above the conveyor and the other positioned6.5 inches above the conveyor. The peak intensity of UVA (320 to 390 nm)and UVV (395 to 445 nm) in the curing line was 0.239 Watts/cm² and ofUVV was 0.416 Watts/cm², respectively, as measured using UV Power Puck™electro-optic radiometers. The UV conveyor curing line had a nitrogenatmosphere in which the oxygen level was less than 100 ppm.

Part E: Preparation of Ordered Coating by Exposure to A Magnetic Field

Sample Substrate Nos. 9A and 10A, which were coated with the adhesivelayer as described above in Part D, were used in this Part E. Theprocedure of Part D used for Sample Substrate No. 11 was followed toform coatings of coating compositions 2 and 3 on Substrate Nos. 9A and10A, respectively, except that after application of the coatingcomposition and prior to curing, the coated substrate was placed on atemperature controlled hot plate 8 inches beneath a temperaturecontrolled infrared lamp and between the North and South poles of a 0.35Tesla magnet that were separated by a distance of 11 centimeters. Bothtemperature controllers were set to maintain a temperature of fromapproximately 55 to 60° C. The coated substrates were kept under theseconditions for 10 to 15 minutes and subsequently cured as described inPart D.

Example 2

Ophthalmic substrates having an at least partial coating were preparedusing an overmold process as described below.

Step 1

The procedure of Parts A & C of Example 1 were followed to form anovermolding coating composition, except that the essentially all of thesolvent in the coating composition was removed by sparging with air for2 hours prior to adding about 2 weight percent of P/D-3, on a totalweight basis, to produce the overmolding coating composition.

Step 2

A six-base lens prepared from CR-39® monomer was cleaned following theprocedure of Part D, Step 1 of Example 1 except that the lens was driedin an oven at 100° C. for 10 minutes prior to treatment with oxygenplasma.

Step 3

The procedure of Part D, Step 2 of Example 1 was followed to form anorientation facility comprising a coating of an at least partiallyordered photo-orientable polymer network to the lens and a glass mold,except that a 90 second exposure to the linearly polarized ultravioletlight was used.

Step 4

After forming the orientation facilities as described above, the glassmold was positioned on a flat surface with the orientation facilityfacing up. An amount of the overmolding solution sufficient to cover themold surface as poured into the center of the mold. Teflon® circularsleeves were placed on the edges of the mold for use as spacers. Thelens was positioned adjacent the mold such that the orientation facilityon the lens contacted the overmolding solution, and the overmoldingsolution spread out to fill the region between the lens and the mold.Clamps were applied to form an assembly that was placed in an oven at45° C. for 30 minutes to permit the liquid crystal material to at leastpartially align with the orientation facilities. Thereafter, theassembly was placed on the ultraviolet conveyor curing line described inStep 3, Part D of Example 1. After curing, the coated lens was releasedfrom the mold. Examination of the coated lens using the cross-polarfilms described above in Step 3, Part D of Example 1 to observealignment of the coating. Absorption ratio measurements were made forthe coatings (as described below) and dichroism was observed.

The thickness of the overmolded coating was determined as follows. Twocross-sections were obtained from the lens, one near the center of thelens and one near the outer edge of the lens. The cross-sections werecoated with a 1.550 refractive index liquid, placed on a microscopeslide and covered with a slip cover. Measurements of the coatingthickness were then taken using a Leitz polarized light microscope and aSpot digital camera. Based on these measurements, the coating wasdetermined to have a thickness near the center of the lens ranging from127±5 microns to 130±5 microns and a thickness near the outer edge ofthe lens ranging from 118±5 microns to 120±5 microns.

Example 3

An optical bench was used to measure the average absorption ratios foreach of the coated samples prepared in Examples 1 and 2 above asfollows. Each of the coated samples was placed on the optical bench withan activating light source (an Oriel Model 66011 300-Watt Xenon arc lampfitted with a Melles Griot 04 IES 211 high-speed computer controlledshutter that momentarily closed during data collection so that straylight would not interfere with the data collection process, a Schott 3mm KG-2 band-pass filter, which removed short wavelength radiation,neutral density filter(s) for intensity attenuation and a condensinglens for beam collimation) positioned at a 30° angle of incidence to thesurface of the coated substrate.

A broadband light source for monitoring response measurements waspositioned in a perpendicular manner to the surface of the coatedsubstrate. Increased signal of shorter visible wavelengths was obtainedby collecting and combining separately filtered light from a 100-Watttungsten halogen lamp (controlled by a Lambda UP60-14 constant voltagepower supply) with a split-end, bifurcated fiber optical cable. Lightfrom one side of the tungsten halogen lamp was filtered with a SchottKG1 filter to absorb heat and a Hoya B-440 filter to allow passage ofthe shorter wavelengths. The other side of the light was either filteredwith a Schott KG1 filter or unfiltered. The light was collected byfocusing light from each side of the lamp onto a separate end of thesplit-end, bifurcated fiber optic cable, and subsequently combined intoone light source emerging from the single end of the cable. A 4″ lightpipe was attached to the single end of the cable insure proper mixing.

Linear polarization of the light source was achieved by passing thelight from the single end of the cable through a Moxtek, ProfluxPolarizer held in a computer driven, motorized rotation stage (ModelM-061-PD from Polytech, PI). The monitoring beam was set so that the onepolarization plane (0°) was perpendicular to the plane of the opticalbench table and the second polarization plane (90°) was parallel to theplane of the optical bench table. The samples were run in air, at roomtemperature (73° F.±5° F.) maintained by the lab air conditioning systemor a temperature controlled air cell.

To conduct the measurements, the coated substrate was exposed to 6.7W/m² of UVA from the activating light source for 5 to 15 minutes toactivate the photochromic-dichroic compound. An International LightResearch Radiometer (Model IL-1700) with a detector system (Model SED033detector, B Filter, and diffuser) was used to verify exposure prior toeach test. Light from the monitoring source that was polarized in the 0°polarization plane was then passed through coated sample and focused ona 2″ integrating sphere, which was connected to a Ocean Optics 2000spectrophotometer using a single function fiber optic cable. Thespectral information after passing through the sample was collectedusing Ocean Optics OOIBase32 and OOIColor software, and PPG proprietysoftware. While the photochromic-dichroic compound was activated, theposition of the polarizing sheet was rotated back and forth to polarizethe light from the monitoring light source to the 90° polarization planeand back. Data was collected at 3-second intervals during activation.For each test, rotation of the polarizers was adjusted to collect datain the following sequence of polarization planes: 0°, 90°, 90°, 0° etc.

Absorption spectra were obtained and analyzed for each coated substrateusing the Igor Pro software (available from WaveMetrics). The change inthe absorbance for each coated substrate was calculated by subtractingout the 0 time (i.e., unactivated) absorption measurement for eachwavelength tested. Average absorbance values were obtained in the regionof the activation profile where the photochromic response was saturatedor nearly saturated (i.e., the regions where the absorbance did notincrease or did not increase significantly over time) for each coatedsubstrate by averaging the absorbance taken at each time interval foreach coated substrate in this region (for each wavelength extracted wereaveraged of 5 to 100 data points). The average absorbance values in apredetermined range of wavelengths corresponding λ_(max-vis)±5 nm wereextracted for the 0° and 90° polarizations, and the absorption ratio foreach wavelength in this range was calculated by dividing the largeraverage absorbance by the small average absorbance. For each wavelengthextracted, 5 to 100 data points were averaged. The average absorptionratio for the sample was then calculated by averaging these individualabsorption ratios.

For each Sample Substrate listed in Table II, the above-describedprocedure was run twice. The tabled value for the Average AbsorptionRatio represents an average of the results obtained from these two runs.

TABLE II Sample Wavelength of Maximum Average Substrate SampleAbsorption Peak at which Absorption No. Coating No. AR measured Ratio 1A1 500 5.4 1 599 5.4 2B 1 500 5.5 1 601 5.5 3A 2 500 4.9 2 599 4.8 4B 2500 4.7 2 599 4.7 5A 3 497 2.1 3 636 2.8 6B 3 497 2.1 3 638 2.9 7A 4 5902.8 8B 4 625 2.7 9A 2(MAGNETIC) 499 3.0 2(MAGNETIC) 600 3.0 10A 3(MAGNETIC) 497 1.7 3(MAGNETIC) 636 2.2 11C  2 501 2.5 2 595 2.6

Example 4

The average absorption ratio of each photochromic-dichroic compoundsP/D-1 through P/D-3, as well as the average absorption ratio ofPhotosol™ 0265 (“Comparative Compound”), which is commercially availablefrom PPG Industries, Inc. and reported to be 1,3,3,4,5 (or1,3,3,5,6)-pentamethyl-spiro[indoline-2,3-[3H]naphth[2,1-b][1,4]oxazine,was measured using the CELL METHOD. According to the CELL METHOD, theoptical bench and procedure described above in Example 3 for measuringthe average absorption ratio of the coatings was used, except that acell assembly (described below) containing the compound to be tested anda liquid crystal material was positioned on the optical bench (insteadof the coated substrate).

A cell assembly having the following configuration was obtained fromDesign Concepts, Inc. Each of the cell assemblies was formed from twoopposing glass substrates that are spaced apart with a glass bead spacerhaving a diameter of 20 microns±1 micron. The inner surfaces of each ofthe glass substrates had oriented polyimide coating thereon to providefor the alignment of a liquid crystal material as discussed below. Twoopposing edges of the glass substrates were sealed with an epoxysealant, leaving the remaining two edges open for filling. The gapbetween the two glass substrates of the cell assembly was filled with aliquid crystal solution containing one of the Test Materials (i.e, thephotochromic-dichroic compounds (P/D-1 to P/D-3) or the ComparativeCompound). The liquid crystal solution was formed by mixing thefollowing components in the weight percents listed in Table III withheating, if necessary, to dissolve the test material.

TABLE III Component Weight Percent Licristal ™ E7   97-99.5 TestMaterial 0.5-3  

For each Test Material, the above-described procedure was run at leasttwice. The tabled value for the Average Absorption Ratio represents anaverage of the results obtained from the runs. The results of thesetests are present in Table IV below.

TABLE IV Average Example Wavelength Range Absorption Number λ_(max-vis)(nm) +/− 5 nm Ratio (AR) Comparative 623 +/− 5 nm 2.3 Example P/D-1 497+/− 5 nm 6.3 P/D-2 497 +/− 5 nm 5.8 P/D-3 639 +/− 5 nm 5.9

Example 5

The average absorption ratio of the photochromic-dichroic compounds inTable V (below) were determined as set forth above. It will beappreciated by those skilled in that the compound listed in Table V maybe made in accordance with the teachings and examples disclosed hereinwith appropriate modifications, which will be readily apparent to thoseskilled in the art. Further, those skilled in the art will recognizethat various modifications to the disclosed methods, as well as othermethods, can be used in making the named compounds set forth below inTable V.

TABLE V Wavelength Average Range Absorption Compound λ_(max) (nm) RatioName (+/−5 nm) (AR) 3-phenyl-3-(4-(4-(3-piperidin-4-yl- 590 2.0propyl)piperidino)phenyl)-13,13-dimethyl-indeno[2′,3′:3,4]-naphtho[1,2-b]pyran3-phenyl-3-(4-([1,4′]bipiperidinyl-1′-yl)phenyl)-13,13- 513 3.4dimethyl-6-methoxy-7-([1,4′]bipiperidinyl-1′-yl)indeno[2′,3′:3,4]naphtho[1,2-b]pyran3-phenyl-3-(4-(4-phenyl-piperazin-1-yl)phenyl)-13,13- 503 3.9dimethyl-6-methoxy-7-(4-(4-hexylbenzoyloxy)-piperidin-1-yl)indeno[2′,3′:3,4] naphtho[1,2-b]pyran3-phenyl-3-(4-(4-phenyl-piperazin-1-yl)phenyl)-13,13- 499 4.1dimethyl-6-methoxy-7-(4-(4′-octyloxy-biphenyl-4-carbonyloxy)-piperidin-1-yl)indeno[2′,3′:3,4]naphtho[1,2- b]pyran3-phenyl-3-(4-(4-(4-butyl-phenylcarbamoyl)-piperidin-1- 506 5.0 yl)phenyl)-13,13-dimethyl-6-methoxy-7-(4-phenyl-piperazin-1-yl)indeno[2′,3′:3,4] naphtho[1,2-b]pyran3-phenyl-3-{4-(pyrrolidin-1-yl)phenyl)-13,13-dimethyl-6- 628 4.8methoxy-7-(4-(4-(4-(3-phenyl-3-{4-(pyrrolidin-1-yl)phenyl}-13,13-dimethyl-6-methoxy-indeno[2′,3′:3,4]naphtho[1,2-b]pyran-7-yl)-piperadin-1-yl)oxycarbonyl)phenyl)phenyl)cabonyloxy)-indeno[2′,3′:3,4]naphtho[1,2-b]pyran;3-phenyl-3-(4-(4-phenyl-piperazin-1-yl)phenyl)-13,13- 502 6.0dimethyl-6-methoxy-7-{4-[17-(1,5-dimethyl-hexyl)-10,13-dimethyl-2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthren-3-yloxycarbonyloxy]-piperidin-1-yl}- indeno[2′,3′:3,4]naphtho[1,2-b]pyran3-phenyl-3-{4-(pyrrolidin-1-yl)phenyl)-13-[17-(1,5- 529 3.3dimethyl-hexyl)-10,13-dimethyl-2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthren-3-yloxy]-13-ethyl-6-methoxy-7-(4-[17-(1,5-dimethyl-hexyl)-10,13-dimethyl-2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthren-3-yloxycarbonyloxy]-piperadin-1-yl)-indeno[2′,3′:3,4]naphtho[1,2-b]pyran3-phenyl-3-(4-{4-[17-(1,5-dimethyl-hexyl)-10,13-dimethyl- 507 6.02,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthren-3-yloxycarbonyloxy]-piperidin-1-yl}-phenyl)-13-ethyl-13-hydroxy-6-methoxy-7-{4-[17-(1,5-dimethyl-hexyl)-10,13-dimethyl-2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthren-3-yloxycarbonyloxy]-piperidin-1-yl}-)indeno[2′,3′:3,4]naphtho[1,2-b]pyran3-phenyl-3-(4-(4-phenyl-piperazin-1-yl)phenyl)-13,13- 496 5.8dimethyl-6-methoxy-7-(4-(4-(4- hexyloxyphenylcarbonyloxy)phenyl)piperazin-1- yl)indeno[2′,3′:3,4]naphtho[1,2-b]pyran3-phenyl-3-(4-(4-methoxyphenyl)-piperazin-1-yl))phenyl)- 499 6.313,13-dimethyl-6-methoxy-7-(4-(4-(3-phenylprop-2-ynoyloxy)phenyl)piperazin-1-yl)- indeno[2′,3′:3,4]naphtho[1,2-b]pyran3-phenyl-3-(4-(pyrrolidin-1-yl)phenyl)-13-hydroxy-13- 629 6.3ethyl-6-methoxy-7-(4-(4-(4-hexylbenzoyloxy)phenyl)piperazin-1-yl)indeno[2′,3′:3,4]naphtho[1,2-b]pyran3-phenyl-3-(4-(pyrrolidin-1-yl)phenyl)-13,13-dimethyl-6- 646 6.4methoxy-7-(4-(4-(4-hexylbenzoyloxy)benzoyloxy)benzoyloxy)indeno[2′,3′:3,4]naphtho[1,2-b]pyran3-(4-methoxyphenyl)-3-(4-(4-methoxyphenyl)piperazin-1- 499 5.4yl)phenyl)-13-ethyl-13-hydroxy-6-methoxy-7-(4-(4-(4-hexylbenzoyloxy)phenyl)piperazin-1-yl)indeno[2′,3′:3,4]naphtho[1,2-b]pyran2-phenyl-2-{4-[4-(4-Methoxy-phenyl)-piperazin-1-yl]- 571 2.7phenyl}-9-hydroxy-8-methoxycarbonyl-2H-naphtho[1,2- b]pyran2-phenyl-2-{4-[4-(4-Methoxy-phenyl)-piperazin-1-yl]- 590 4.0phenyl}-9-hydroxy-8-(N-(4-butyl-phenyl))carbamoyl-2H-naphtho[1,2-b]pyran 2-phenyl-2-{4-[4-(4-Methoxy-phenyl)-piperazin-1-yl]-566 3.9 phenyl}-9-hydroxy-8-(N-(4-phenyl)phenyl) carbamoyl-2H-naphtho[1,2-b]pyran 2-phenyl-2-{4-[4-(4-Methoxy-phenyl)-piperazin-1-yl]-583 4.2 phenyl}-benzofuro[3′,2′:7,8] benzo[b]pyran2-phenyl-2-{4-[4-(4-Methoxy-phenyl)-piperazin-1-yl]- 510 4.1phenyl}-benzothieno[3′,2′:7,8] benzo[b]pyran1,3,3-trimethyl-6′-(4-ethoxycarbonyl)-piperidin-1-yl)- 590 6.0spiro[indoline-2,3′-3H-naphtho[2,1-b][1,4]oxazine]1,3,3-trimethyl-6′-(4-[N-(4-butylphenyl)carbamoyl]- 590 7.8piperidin-1-yl)-spiro[indoline-2,3′-3H-naphtho[2,1- b][1,4]oxazine]3-phenyl-3-(4-pyrrolidinylphenyl)-13,13-dimethyl-6- 627 6.5methoxy-7-(4-(4-(4-(4-(6-(4-(4-(4-nonylphenylcabonyloxy)phenyl)oxycarbonyl)phenoxy)hexyloxy)phenyl)piperazin-1-yl)indeno[2′,3′:3,4] naphtho[1,2- b]pyran1,3,3-trimethyl-6′-(4-(4-methoxyphenyl)piperazin-1- 586 8.3yl)-spiro[indoline-2,3′-3H-naphtho[2,1- b][1,4]oxazine];1,3,3-trimethyl-6′-(4-(4-hydroxyphenyl)piperazin-1- 587 7.0yl)-spiro[indoline-2,3′-3H-naphtho[2,1- b][1,4]oxazine];

Example 6

Electro-optic cell assemblies according to various non-limitingembodiments disclosed herein were prepared as follows.

Step 1

Unpolished float glass slides measuring 25×50×1.1 mm having an indiumtin oxide (“ITO”) coating on one surface, R_(s)≦100Ω, obtained fromDelta Technologies, Limited, were used. The ITO coated surface of twoslides was further coated polyimide coating solution that was preparedas follows. The components listed in Table VI, were added in the orderlisted to a beaker. After all of the components were added, thecomposition was mixed until the components were dissolved.

TABLE VI Components Weight (grams) PI2255⁽¹⁾ 80 3-ethoxypropanol 80NMP⁽²⁾ 320 ⁽¹⁾Polyimide available from DuPont. ⁽²⁾N-methylpyrrolidone.

The polyimide coating solution was applied to the ITO coated surface ofthe glass slides by spin coating. 1.5 milliliters (mL) of the coatingsolution was dispensed onto the glass slides spinning at 1000 rpm for 90seconds.

Step 2

The coated slides of Step 1 were held at 130° C. for 15 minutes, afterwhich the temperature was increased to 250° C. and held at the elevatedtemperature for at least 90 minutes. The slides were removed and allowedto cool to room temperature.

Step 3

The coated slides of Step 2 were put into a holder with the coated sideup. The surface of the coated slide was gently brushed with a velvetbrush in the lengthwise direction several times to remove any dirt.Afterwards, the coated slide was brushed ten more times applying enoughpressure to form parallel groves in the coating. Glass spheres having adiameter of 20 microns were applied to one of the coated slides to serveas spacers when the other coated slide was positioned to form a parallelrubbed cell having a portion of each slide extending over the other sothat electrical connections could be made to each slide. The resultingelectro-optic cell assembly was clamped.

Step 4

The lengthwise edges of the electro-optic cell assembly of Step 3 werecoated with Devon Epoxy Glue, the components of which had beenpreviously mixed in a 1:1 ratio. The glued electro-optic cell assemblywas left at room temperature for one hour and then heated for at leastone hour at least 1000 centigrade.

Step 5

The electro-optic cell assembly of Step 4 was filled with a photochromicliquid crystal coating solution using a capillary tube to apply thesolution until the cell assembly was filled. The photochromic liquidcrystal solution was prepared by the addition of a small amount of P/D-3to a few drops of Licristal™ E7 available from EM Industries.

Example 7

The average absorption ratios for the electro-optic cell assemblies ofExample 4 were determined as follows. The aforedescribed optical benchwas modified with a conductive electro-optic cell-mounting device thatserved to hold the electro-optic cell in place and allow an electricalflow of 8 volts DC applied through a Lambda Model LLS5018 power supplyto pass through it. The modified optical bench was used to obtain theresponse measurements and derive absorbance ratios of P/D-3 in theLicristal™ E7 liquid crystal solution used in the electro-optic cellassembly following the procedure of Example 3, except as follows.

The electro-optic cell assembly was activated for 10 minutes with nocurrent applied and the average absorption ratio was determined.Application of an 8-volt DC flow to the electro-optic cell assemblywhile still being activated by the filtered Xenon light was done for anadditional 10 minutes and the average absorption ratio was determinedagain. The results are listed in Table VII.

TABLE VII Wavelength of Maximum Voltage Absorption Peak at which AverageState AR measured Absorption Ratio No Voltage 501 3.4 No Voltage 647 5.3Voltage 501 1.7 Voltage 647 1.5

The results of Table VII show that the electro-optic cell assemblyexhibited absorptions ratios from 3.4 to 5.3 over the wavelength rangeof 501 to 647 nm while exposed to photochromic activating radiationwithout the application of voltage and that the application of voltage(8 volts of direct current) caused a reduction in the average absorptionratios to 1.7 to 1.5 over the same wavelength range while the exposureto photochromic activating radiation continued.

It is to be understood that the present description illustrates aspectsof the invention relevant to a clear understanding of the invention.Certain aspects of the invention that would be apparent to those ofordinary skill in the art and that, therefore, would not facilitate abetter understanding of the invention have not been presented in orderto simplify the present description. Although the present invention hasbeen described in connection with certain embodiments, the presentinvention is not limited to the particular embodiments disclosed, but isintended to cover modifications that are within the spirit and scope ofthe invention, as defined by the appended claims.

1. A composite optical element comprising: a substrate; an at leastpartially ordered polymeric sheet connected to at least a portion of thesubstrate; and at least one thermally reversible photochromic-dichroiccompound that is at least partially aligned with at least a portion ofthe at least partially ordered polymeric sheet and has an averageabsorption ratio greater than 2.3 in the activated state as determinedaccording to CELL METHOD.
 2. The composite optical element of claim 1wherein the at least partially ordered polymeric sheet is chosen from astretched polymer sheet, an at least partially ordered liquid crystalpolymer sheet, and a photo-oriented polymer sheet.
 3. The compositeoptical element of claim 1 further comprising a first rigid polymericsheet interposed between the substrate and the at least partiallyordered polymeric sheet and a second rigid polymeric sheet positionedover the at least partially ordered polymeric sheet.
 4. The compositeoptical element of claim 1 further comprising at least one additional atleast partially ordered polymeric sheet connected to at least a portionof the substrate.
 5. The composite optical element of claim 1, wherein:the at least one sheet connected to at least a portion of the substratecomprises: an at least partially ordered liquid crystal polymer havingat least a first general direction; at least one at least partiallyordered liquid crystal material having at least a second generaldirection that is generally parallel to at least the first generaldirection distributed within at least a portion of the liquid crystalpolymer; and at least one photochromic-dichroic compound that is atleast partially aligned with at least a portion of the at least one atleast partially ordered liquid crystal material.